Pentacyclic anion salts or tetrazapentalene derivatives and their uses as ionic conducting materials

ABSTRACT

The invention relates to ionic compounds in which the anionic load has been delocalized. A compound disclosed by the invention includes an anionic portion combined with at least one cationic portion M m+  in sufficient numbers to ensure overall electronic neutrality; the compound is further comprised of M as a hydroxonium, a nitrosonium NO + , an ammonium —NH 4   + , a metallic cation with the valence m, an organic cation with the valence m, or an organometallic cation with the valence m. The anionic load is carried by a pentacyclical nucleus of tetrazapentalene derivative bearing electroattractive substituents. The compounds can be used notably for ionic conducting materials, electronic conducting materials, colorant, and the catalysis of various chemical reactions.

The present invention has for its object ionic compounds in which theionic charge is carried by a pentacyclic nucleus or a derivative oftetrazapentalene, and their uses.

Derivatives of non-nucleophilic or slightly basic anions have anincreasing importance in all applications of chemistry to stabilize oractivate various cationic charges such as those of coloring materials orintermediate species in polymerizations. They also act as intermediatesfor various reactions of organic chemistry. In electrochemistry, mediaother than water are more and more relied upon for applications such asprimary or secondary generators, supercapacitances, systems ofmodulation of light. The introduction of a weak ionic conductivity inthe usual materials (polymers, combustible liquids), enables to disperseelectrostatic charges.

The mainly known derivatives are those derived from coordination anionsof the type BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, however, they have a limited stabilitydue to the dissociation equilibrium releasing the fluoride anion and thecorresponding Lewis acid, the two causing parasite reactions andpresenting some toxicity. The perchlorate anion ClO₄ ⁻ is thermallyunstable and dangerous.

On the other hand, anions derived from perfluoroalkylsulfonates andespecially bis(perfluoroalkylsulfonyl)imides are known, which presentinteresting properties. However, the chemistry of these compounds isrelatively difficult to control, in particular the preparation ofprecursors of the type R_(F)SO₂—. It is also known that hydrocarbonssuch as cyclopentadiene easily form salts by deprotonation, however,they acidity and the stability of the anion remain very insufficient(pKa≈16).

The inventors have found surprisingly that the properties of compoundsderived from cyclopentadiene were considerably modified when a carbon ofthe cycle was replaced by a more electronegative element than carbon, orwhen an electronegative substituent was fixed to a carbon atom of thecycle. Depending on the choice of substituents, these compounds givesalts which are easily soluble and strongly dissociated, including inorganic media which are less polar than water. These salts haveinteresting properties for a number of applications and theirpreparation relies on materials which are more easily accessible. It isfor example possible to obtain stable anionic heterocycles incorporatingsmaller quantities, which may even be null, of fluorine, or fromfluorinated compounds which are easily accessible.

It is known and particularly interesting to introduce ionic groups inmolecules or organic polymers having various functions. Coulombic forcescorrespond, indeed, to the stronger interactions which are available atthe molecular level, and the ionic groups modify in the most noted waythe molecules to which they are bonded. Coloring materials which aremade soluble in water by means of sulfonate or carboxylate functions maybe mentioned. However, the groups of this type —CO₂ ⁻1/mM^(m+) or —SO₃ ⁻1/mM^(m+) are not dissociated, and they do not induce solubility insolvents other than water or certain highly polar protic solvents suchas light alcohols, which considerably restrict the scope of theirutilization.

The possibilities of substitution associated with the chemistry ofcompounds derived from pentagonal cycles of the invention therefore alsoenable to introduce ionic groups in various molecules.

It is consequently an object of the present invention to provide afamily of ionic compounds having a good solubility and good dissociationwithout having to rely on complex modifications of the startingmolecule. The precursors of the molecules of the invention are generallyeasily accessible.

BRIEF DESCRIPTION OF THE FIGURE

FIG. 1 is a cycling curve showing utilization u verses the number ofcycles c in a battery according to the invention.

An ionic compound of the present invention comprises at least oneanionic part associated to at least one cationic part M in sufficientnumber to ensure the electronic neutrality of the whole, characterizedin that M is a hydroxonium, a nitrosonium NO⁺, an ammonium —NH₄ ⁺, ametallic cation having a valency m, an organic cation having a valency mor an organometallic cation having a valency m, and in that the anionicpart is pentacyclic or derived from tetrazapentalene and corresponds toone of the following formulae:

in which the groups —X_(i)— represent independently from one another agroup selected from —N═, —N—, —C(Y_(c))═, ═C(Y_(c))—, —S(═O)(Qs)═,—S(Qs)═ or —P(Q′)(Q″)═, it being understood that among the five groups—X_(i)— forming the cycle, at most four groups —X_(i)— comprise anhydrogen atom, at most two groups —X_(i)— comprise a sulfur atomprovided they are not adjacent on the cycle, at most one group —X_(i)—comprise a phosphorus atom, and:

Q′ and Q″ represent independently from one another a C₁-C₈ perhaloalkylor perhaloalkenyl radical, a C₆-C₁₂ aryl or alkylaryl radical, possiblyhalogenated, each may contain oxa, thia, aza substituents;

Q_(s) is a radical selected from:

a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylarylradicals, alicyclic or heterocyclic radicals, including polycyclicradicals, said radicals being possibly halogenated or perhalogenatedand/or possibly carrying at least one functional ether, thioether,amine, imine, amide, carboxyl, carbonyl, isocyanate, isothiocyanate,hydroxy functional group;

b) monocyclic, polycyclic or condensed aromatic radicals in which thearomatic nuclei and/or at least one substituent of a nucleus compriseheteroatoms such as nitrogen, oxygen, sulfur;

c) polymer radicals,

d) radicals having one or more cationic ionophoric groups and/or one ormore anionic ionophoric groups;

Y_(c) or Y represent H, or a group attracting electrons selected fromthe group consisting of:

F, Cl, Br, —C≡N, —S—C≡N, —N═C═S, —N═C═O, —NO₂, C_(n)F_(2n+1)—C_(n)F_(2n+1)—O—, C_(n)F_(2n+1)—CH₂—, —OC₂F₄H, —SCF₃, —SC_(n)F_(2n+1),—SC₂F₄H, —O— CF═CF₂, —SCF═CF₂, FSO₂;

radicals QSO₂—, —CO₂Q, Q—N—SN₂—, QCO—, in which Q is selected from thesubstituents defined about for Q_(s);

radicals comprising one or more aromatic nuclei possibly containing atleast one nitrogen, oxygen, sulfur or phosphorus atoms, said nuclei maypossibly be condensed nuclei and/or the nuclei may possibly carry atleast one substituent selected from halogens, —CN, —NO₂, —SCN, —N₃,CF₂═CF—O—, radicals RF— and R_(F)CH₂— in which R_(F) is a perfluoroalkylradical having 1 to 12 carbon atoms, fluoroalkyloxy groups,fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxa-alkenyl,aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl radicals, polymerradicals, radicals having at least one cationic ionophoric group and/orat least one anionic ionophoric group;

or two substituents from Y_(c), Q_(s), Q′ and Q″ on the one hand and twosubstituents Y on the other hand, together forming a cycle having 4 to 8chains, said cycle possibly being of aromatic conjugated nature;

or one from the substituents Y, Y_(c) or Q_(s) is a multivalent radical(including a dendrimer) connected to at least one pentacyclic anionicgroup or derived from tetrazapentalene as defined above;

or one of the substituents Y, Y_(c) or Q_(s) represent a recurring unitof a polymer.

In a compound of the present invention, the cation may be a metalliccation selected from cations of alkali metals, cations of alkali-earthmetals, cations of transition metals, cations of trivalent metals,cations of rare earths. By way of example, Na⁺, Li⁺, K⁺, Sm³⁺, La³⁺,Ho³⁺, Sc³⁺, Al³⁺, Y³⁺, Yb³⁺, Lu³⁺, Eu³⁺ may be mentioned.

The cation may also be an organometallic cation, for example ametallocenium. By way of example, cations derived from ferrocene,titanocene, zirconocene, indenocenium or an arene metallocenium, cationsof transition metals complexed with ligands of the phosphone typepossibly having a chirality, organometallic cations having one or morealkyl or aryl groups covalently fixed to an atom or a group of atomssuch as methylzinc, phenylmercury, trialkyltin or trialkyllead cations,may be mentioned. The organometallic cation may be part of a polymerchain.

According to a variant of the invention, the compounds of the inventionhave an organic cation selected from the group consisting of cationsR₃O⁺ (oxonium), NR₄ ⁺ (ammonium), RC(NHR₂)₂ ⁺ (amidinium), C(NHR₂)₃ ⁺(guanidinium), C₅R₆N⁺ (pyridinium), C₃R₅N₂ ⁺ (imidazolium), C₃R₇N₂ ⁺(imidazolinium), C₂R₄N₃ ⁺ (triazolium), SR₃ ⁺ (sulfonium), PR₄ ⁺(phosphonium), IR₂ ⁺ (iodonium), (C₆R₅)₃C⁺ (carbonium). In a givencation, the radicals R may all be identical. However, a cation may alsoinclude radicals R which may be different from one another. The radicalR may be a H or it may be selected from the following radicals:

alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl,thia-alkyl, thia-alkenyl, sila-alkyl, sila-alkenyl, aryl, arylalkyl,alkylaryl, alkenylaryl, dialkylamino and dialkylazo radicals;

cyclic or heterocyclic radicals possibly comprising at least one lateralchain comprising heteroatoms such as nitrogen, oxygen, sulfur;

cyclic or heterocyclic radicals possibly comprising heteroatoms in thearomatic nucleus;

groups comprising a plurality of aromatic or heterocyclic nuclei,condensed or non-condensed, possibly containing at least one nitrogen,oxygen, sulfur or phosphorus atom.

When an onium cation carries at least two radicals R which are differentfrom H, these radicals may together form a cycle which may be aromaticor non-aromatic, eventually enclosing the center carrying the cationiccharge.

When the cationic part of a compound of the invention is an oniumcation, it may be in the form of an independent cationic group which isonly bound to the anionic part by the ionic bond between the positivecharge of the cation and the negative charge of the pentacyclic anionicpart or it may be derived from a tetrazapentalene. In this case, thecationic part may be part of a recurring unit of a polymer.

An onium cation may also be part of a substituent Y, Y_(c) or Q_(s)carried by the pentacyclic anionic center or derived fromtetrazapentalene. In this case, a compound of the invention constitutesa zwitterion.

When the cation of a compound of the invention is an onium cation, itmay be selected so as to introduce in the compound, substituents capableof giving specific properties to said compound. For example, the cationM⁺ may be a cationic heterocycle with aromatic character, including atleast one nitrogen atom which is alkylated in the cycle. By way ofexample, an imidazolium, a triazolium, a pyridinium, a4-dimethylamino-pyridinium may be mentioned, said cations possiblycarrying a substituent on the carbon atoms of the cycle. Among thesecations, those which give an ionic compound according to the inventionin which the melting point is lower than 150° C. are particularlypreferred. Such a compound having a low melting temperature isparticularly useful for preparing materials with protonic conduction. Aparticularly preferred material with protonic conduction comprises acompound according to the invention in which the cation is formed byaddition of a proton on the nitrogen of an imidazoline, an imidazole ora triazole, as well as the corresponding nitrogenated base in aproportion of 0.5 to 10 in molar ratio.

A compound of the invention in which the cation M is a cationic grouphaving a bond —N═N—, —N═N⁺, a sulfonium group, an iodonium group, or asubstituted or non-substituted arene-ferrocenium cation, possiblyincorporated in a polymeric network, is interesting insofar as it can beactivated by a source of actinic energy of suitable wavelength. Asparticular examples of such compounds, there may be mentioned those inwhich the cation is a diaryliodonium cation, a dialkylaryliodoniumcation, a triarylsulfonium cation, a trialkylaryl sulfonium cation, or aphenacyl-dialkyl sulfonium cation which is substituted ornon-substituted. The above cations may be part of a polymer chain.

The cation M of a compound of the invention may include a group2,2′[azobis(2-2′-imidazolinio-2-yl)propane]²⁺ or2,2′-azobis(2-amidiniopropane)²⁺. The compound of the invention is thencapable of releasing, under the action of heat or an ionizing radiation,radicals which enable to initiate reactions of polymerization, ofcross-linking or, in a general manner, chemical reactions involving freeradicals. Moreover, these compounds are easily soluble in polymeric ormonomeric organic solvents even those of low polarity, contrary to theanion derivatives of the type Cl⁻ usually associated with these type ofcompounds. They have a negligible vapour pressure contrary to the otherfree radical initiators of the peroxide or azo type, which is aconsiderable advantage for providing polymers in thin films, thevolatility of the initiator having as a consequence a bad polymerizationor cross-linking of the film surface.

According to an embodiment of the invention, at least one of thesubstituents Q_(s) or Q is selected from alkyl, alkenyl, oxa-alkyl,oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl or thia-alkenyl radicalshaving 1 to 24 carbon atoms, or from aryl, arylalkyl, alkylaryl oralkenylaryl radicals having 5 to 24 carbon atoms, or from alkyl oralkenyl radicals having 1 to 12 carbon atoms and possibly comprising atleast one heteroatom O, N or S in the main chain or in a lateral chain,and/or possibly carrying an hydroxy group, a carbonyl group, an aminegroup, a carboxyl group. Q_(s) or Q may also be part of apoly(oxyalkylene) radical or a polystyrene radical.

Another category of compounds according to the invention comprisescompounds in which one of the substituents Y, Y_(c) or Q_(s) has atleast one anionic ionophoric group and/or at least one cationicionophoric group. The anionic group may for example be a carboxylicfunction (—CO₂ ⁻), a sulfonate function (—SO₃ ⁻), a sulfonimide function(—SO₂NSO₂—) or a sulfonamide function (—SO₂N—). The cationic ionophoricgroup may for example be an iodonium, sulfonium, oxonium, ammonium,amidinium, guanidinium, pyridinium, imidazolium, imidazolinium,triazolium, phosphonium or carbonium group. The cationic ionophoricgroup may totally or partially behave as cation M.

When at least one of these substituents Y, Y_(c) or Q_(s) includes atleast one ethylenic unsaturation and/or one condensable group and/or onethermally, photochemically or ionically dissociable group, the compoundsof the invention are reactive compounds which may be subject topolymerizations, cross-linkings or condensations, possibly with othermonomers. They may also be used to fix ionophoric groups on polymerscarrying a suitable reactive function.

In a compound of the invention, at least one of the substituents Y,Y_(c) or Q_(s) may be a mesomorphous group or a chromophore group or aself-doped electronically conductive polymer or a hydrolyzablealkoxysilane.

A substituent Y, Y_(c) or Q_(s) may include a group capable of trappingfree radicals, for example a hindered phenol or a quinone.

A substituent Y, Y_(c) or Q_(s) may also include a dissociating dipole,for example an amide function, a sulfonamide function or a nitrilefunction.

A substituent Y, Y_(c) or Q_(s) may also include a redox couple, forexample a disulfide group, a thioamide group, a ferrocene group, aphenothiazine group, a bis(dialkylaminoaryl) group, a nitroxide group oran aromatic imide group.

A substituent Y, Y_(c) or Q_(s) may also comprise an optically activegroup or a complexing ligand.

Another category of compounds comprises compounds in which Y or Y_(c)represent an amino acid, or an optically or biologically activepolypeptide.

According to a specific embodiment, the substituents Y or Y_(c) of acompound of the invention are different from a perfluoroalkylsulfonylgroup when M is a metallic cation.

In a compound of the invention, one of the substituents Y, Y_(c) orQ_(s) may be a radical having a valency v higher than two, comprising ateach of its free ends an anionic pentacyclic group. Preferably, saidmultivalent radical comprises at least one —SO₂— group, one —CO— group,a perfluoroalkylene group having 1 to 8 carbon atoms, a phenylene grouppossibly substituted with heteroatoms, a group —(W═W)_(n)— or a cationicgroup —(W═W)_(n)—W⁺—, in which W is a nitrogen atom or a CR group inwhich R represents an organic radical and 0≦n≦5, R being a hydrogen atomor an alkyl radical having 1 to 8 carbon atoms, or two substituents Rtogether forming a cycle. In this case, the negative charges which arepresent on the pentacyclic anionic part or the part which is derivedfrom tetrazapentalene of the compound of the invention should becompensated by the appropriate number of cations or ionophoric cationicgroups M.

One of the substituents Y, Y_(c) or Q_(s) may also represent a recurringunit of a polymer chain. The compound of the invention may then be inthe form of a polymer in which at least part of the recurring unitscarry a lateral group in which a pentacyclic anionic group or a groupderived from tetrazapentalene is fixed.

According to an embodiment of the invention, Y or Y_(c) isadvantageously selected from the group consisting of —CN,—OC_(n)F_(2n+1), —OC₂F₄H, —SC_(n)F_(2n+1) and —SC₂F₄H, —O—CF═CF₂,—SCF═CF₂, n being a whole number from 1 to 8. Y or Y_(c) may also be aradical C_(n)F_(2n+1)CH₂—, n being a whole number from 1 to 8, or fromheterocycles in particular those derived from pyridine, pyrazine,pyrimidine, oxadiazole, thiadiazole, which are fluorinated ornon-fluorinated.

The ionic compounds of the present invention comprise at least oneionophoric group in which substituents of various natures are fixed. Inview of the very large possible choice of substituents, the compounds ofthe invention enable to provide properties of ionic conduction in mostliquid or polymeric organic media having a polarity, which may even bevery low. The applications are important in the field ofelectrochemistry, in particular for storing energy in primary orsecondary generators, in supercapacitances, in combustible batteries andin electroluminescent diodes. The compatibility of the ionic compoundsof the present invention with polymers or organic liquids enables toprovide noted antistatic properties, even when the content in ioniccompound is extremely low. The compounds of the invention which arepolymers, as well as polymeric compounds obtained from compounds of theinvention having the property of polymerizing or copolymerizing, havethe above-mentioned properties with the advantage of possessing a fixedanionic charge. This is why another object of the present inventionconsists of an ionic conductive material made of an ionic compound ofthe present invention in solution in a solvent.

In an embodiment, the ionic compound used for preparing an ionicallyconductive material is selected from compounds in which the cation isammonium, or a cation derived from a metal, in particular lithium orpotassium, zinc, calcium, rare earth metals, or an organic cation, suchas a substituted ammonium, an imidazolium, a triazolium, a pyridinium, a4-dimethylamino-pyridinium, said cations possibly carrying a substituenton the carbon atoms of the cycle. The ionically conductive material thusobtained has a high conductivity and solubility in solvents, due to weakinteractions between the positive charge and the negative charge. Itsfield of electrochemical stability is wide, and it is stable in reducingas well as oxidizing media. Moreover, the compounds which have anorganic cation and a melting point lower than 150° C., in particularimidazolium, triazolium, pyridinium, 4-dimethylamino-pyridiniumcompounds have an intrinsic high conductivity, even in the absence ofsolvent, when they are in molten phase.

The properties of the ionically conductive material may also be adaptedby the choice of substituents Y, Y_(c) or Q on the one hand, and Q_(s)on the other hand.

The choice for Q or Q_(s) of an alkyl group, an aryl group, an alkylarylgroup or an arylalkyl group enables to induce in the ionicallyconductive material, properties of the type mesogene, in particularalkyl groups of 6 to 20 carbon atoms, arylalkyl groups, in particularthose containing a biphenyl unit, which produce phases of the typeliquid crystal. Properties of conduction in phases of the type liquidcrystal, nematic, cholesteric or discotic, are interesting forapplications relative to optical postings or to reduce the mobility ofanions in electrolytes, in particular in polymer electrolytes, withoutaffecting the mobility of the cations. This particularity is importantfor applications in electrochemical generators, in particular thoseinvolving lithium cations.

When Q or Q_(s) is a mesomorphous group or a group comprising at leastone ethylenic unsaturation and/or a condensable group and/or a groupwhich is thermally, photochemically or ionically dissociable, theionically conductive material easily forms polymers or copolymers whichare polyelectrolytes, either intrinsically when the polymer carries thesolvating groups, or by addition of a polar solvent of the liquid orpolymer type, or by mixture with such a solvent. These products have aconductivity which is solely due to the cations, which constitutes avery useful property for applications of the electrochemical generatortype. When used in low molar fraction in a copolymer, they induce stableantistatic properties which are little dependent on humidity and promotethe fixation of cationic coloring materials, this property being usefulfor textile fibers and lasers with coloring materials.

The presence of a substituent Q or Q_(s) which is a self-dopedelectronically conductive polymer improves the stability of theionically conductive material with respect to exterior agents. Theconductivity is stable in time, even at elevated temperatures. Incontact with metal, these materials give interface resistances which arevery weak and in particular protect ferrous metals or aluminum againstcorrosion.

When a substituent Q or Q_(s) is a hydrolyzable alkoxysilane, theionically conductive material may form stable polymers by the simplemechanism of hydrolysis-condensation in the presence of water, therebyenabling to treat surfaces of oxides, silica, silicates, in particularglass, to produce properties of surface conduction, antistaticproperties, or to promote the adhesion of polar polymers.

When a substituent Y, Y_(c) or Q_(s) is a group comprising a freeradical trap such as a hindered phenol, or a quinone, the ionicallyconductive material has the following advantages and properties: it actsas antioxidant with no volatility and is compatible with polar monomersand polymers, to which it additionally gives antistatic properties.

When a substituent Y, Y_(c) or Q_(s) comprises a dissociating dipolesuch as an amide, a sulfonamide or a nitrile, the ionically conductivematerial has an improved conductivity in media of low and mediumpolarity, in particular in solvating polymers which enables to minimize,even to suppress, the addition of solvents or volatile plasticizingagents.

The presence of a substituent Y, Y_(c) or Q_(s) which contains a redoxcouple such as a disulfide, a thioamide, a ferrocene, a phenothiazine, abis(dialkylaminoaryl) group, a nitroxide, an aromatic imide, enables toproduce in the ionically conductive materials, properties of a redoxshuttle which are useful as an element of protection and equalization ofcharge of electrochemical generators, in photoelectrochemical systems,in particular for the conversion of light into electricity in systems ofmodulation of light of the electrochrome type.

The presence of a substituent Y, Y_(c) or Q_(s) which is a complexingligand in an ionically conductive material enables to chelate metalliccations, in particular those which possess an elevated charge (2, 3 and4), in the form of soluble complex in organic media, including inaprotic media, and enables the transport of these cations in particularin the form of anionic complex, in solvating polymers. The metalliccations of elevated charge are indeed immovable in solvating polymers.This type of complexing gives with certain cations of transition metals(Fe, Co . . . ) or certain rare earths (Ce, Eu . . . ) particularlystable redox couples.

The ionically conductive materials containing a compound of theinvention in which a substituent Q or Q_(s) is an alkyl or alkenylsubstituent which contains at least one heteroatom selected from O, N orS have a complexing and plasticizing capacity, in particular in polarpolymers and especially polyethers. The heteroatoms N and S areselectively complexing for cations of transition metals, Zn and Pb.

When a substituent alkyl or alkenyl Q or Q_(s) additionally carries anhydroxy group, a carbonyl group, an amine group, a carboxyl group, anisocyanate group or a thioisocyanate group, the ionic compound of theinvention may give by polycondensation a polymer or a copolymer and theionically conductive material which contains such a polymer or copolymerhas polyelectrolytic properties.

The presence, in the ionically conductive material of the invention, ofa compound in which a substituent Q or Q_(s) is selected from aryl,arylalkyl, alkylaryl, alkylaryl or alkenylaryl radicals, in which thelateral chains and/or the aromatic nuclei comprise heteroatoms such asnitrogen, oxygen, sulfur, improves dissociation and increases thepossibility of forming complexes depending on the position of theheteroatom (pyridine) or the possibility to give by duplicativeoxidation, conjugated polymers or copolymers (pyrrole, thiophene).

When the ionically conductive material contains a compound of theinvention in which a substituent Y, Y_(c) or Q_(s) represents arecurring unit of a polymer chain, the material constitutes apolyelectrolyte.

A compound of the invention in which the substituent Y, or Y_(c) isselected from the group consisting of —OC_(n)F_(2n+1), —OC₂F₄H,—SC_(n)F_(2n+1) and —SC₂F₄H, —OCF═CF₂, —SCF═CF₂, n being a whole numberfrom 1 to 8, is a precursor of stable monomers and polymers, inparticular towards oxygen even at temperatures higher than 80° C. whendealing with polymers. An ionically conductive material which containssuch a compound is therefore particularly suitable as the electrolyte ofa combustible battery.

An ionically conductive material of the present invention comprises anionic compound of the present invention in solution in a solvent.

The solvent may be an aprotic liquid solvent, a polar polymer or amixture thereof.

The aprotic liquid solvent is selected for example from linear ethersand cyclic ethers, esters, nitrites, nitro derivatives, amides,sulfones, sulfolanes, alkylsulfamides and partially halogenatedhydrocarbons. The solvents which are particularly preferred are diethylether, dimethoxyethane, glyme, tetrahydrofurane, dioxane,dimethyltetrahydrofurane, methyl or ethyl formate, propylene or ethyleneis carbonate, alkyl carbonates (such as dimethyl carbonate, diethylcarbonate and methylpropyl carbonate), butyrolactones, acetonitrile,benzonitrile, nitromethane, nitrobenzene, dimethylformamide,diethylformamide, N-methylpyrrolidone, dimethylsulfone, tetramethylenesulfone and tetraalkylsulfonamides having 5 to 10 carbon atoms.

The polar polymer may be selected from cross-linked or non-cross-linkedsolvating polymers, which may carry grafted ionic groups. A solvatingpolymer is a polymer which includes solvating units containing at leastone heteroatom selected from sulfur, oxygen, nitrogen and fluorine. Byway of example of solvating polymers, there may be cited polyethers oflinear structure, comb or blocks, which may form a network, based onpoly(ethylene oxide), or copolymers containing the unit ethylene oxideor propylene oxide or allylglycidylether, polyphosphazenes, cross-linkednetworks based on polyethylene glycol cross-linked with isocyanates ornetworks obtained by polycondensation and carrying groups which enablethe incorporation of cross-linkable groups. Block copolymers in whichcertain blocks carry functions which have redox properties may also becited. Of course, the above list is non-limiting, and all the polymershaving solvating properties may be used.

An ionically conductive material of the present invention maysimultaneously comprise an aprotic liquid solvent selected from theaprotic liquid solvents mentioned above and a polar polymer solventcomprising units containing at least one heteroatom selected fromsulfur, nitrogen, oxygen and fluorine. It may comprise from 2 to 98%liquid solvent. By way of example of such a polar polymer, polymerswhich mainly contain units derived from acrylonitrile, vinylidenefluoride, N-vinylpyrrolidone or methyl methacrylate may be mentioned.The proportion of aprotic liquid in the solvent may vary from 2%(corresponding to a plasticized solvent) to 98% (corresponding to agelled solvent).

An ionically conductive material of the invention may additionallycontain a salt which is well known to be used in the prior art forpreparing ionically conductive material. Among the salts which may beused in admixture with an ionic compound of the invention, a saltselected from perfluoroalcanesulfonates,bis(perfluoroalkylsulfonyl)imides, bis(perfluoroalkylsulfonyl)methanesand tris(perfluoroalkylsulfonyl)methanes are particularly preferred.

Of course, an ionically conductive material of the invention mayadditionally contain additives known to be used in this type of materialand for example mineral or organic charges in the form of powder orfibers.

An ionically conductive material of the invention may be used aselectrolyte in an electrochemical generator. Thus, another object of thepresent invention is an electrochemical generator comprising a negativeelectrode and a positive electrode both separated by an electrolyte,characterized in that the electrolyte is an ionically conductivematerial as defined above. According to a particular embodiment, such agenerator comprises a negative electrode consisting of metallic lithium,or an alloy thereof, possibly in the form of nanometric dispersion inlithium oxide, or a double nitride of lithium and of a transition metal,or an oxide of low potential having the general formulaLi_(1+y+x/3)Ti_(2−x/3)O₄ (0≦x ≦1, 0≦y≦1), or carbon and carbonatedproducts produced by pyrolysis of organic materials. According toanother embodiment, the generator comprises a positive electrodeselected from vanadium oxides VO_(x) (2≦x≦2,5), LiV₃O₈,Li_(y)Ni_(1−x)Co_(x)O₂, (0≦x<1; 0≦y≦1), spinels of manganeseLi_(y)Mn_(1−x)M_(x)O₂ (M=Cr, Al, V, Ni, 0≦x≦0,5; 0≦y≦2), organicpolydisulfides FeS, FeS₂, iron sulfate Fe₂(SO₄)₃, phosphates andphosphosilicates of iron and lithium of olivine structure, orsubstituted products wherein iron is replaced by manganese, used aloneor in admixtures. The collector of the positive electrode is preferablyaluminum.

An ionically conductive material of the present invention may also beused in a supercapacitance. Another object of the present invention isconsequently a supercapacitance utilizing at least one carbon electrodeof high specific surface, or an electrode containing a redox polymer inwhich the electrolyte is an ionically conductive material such asdefined above.

An ionically conductive material of the present invention may also beused for doping, p or n, an electronically conductive polymer and thisuse constitutes another object of the present invention.

In addition, an ionically conductive material of the present inventionmay be used as an electrolyte is an electrochrome device. Anelectrochrome device in which the electrolyte is an ionically conductivematerial according to the invention is another object of the presentinvention.

It has been observed that the strong dissociation of ionic species ofthe compounds of the invention results in a stabilization ofcarbocations, in particular those in which there is a conjugation withoxygen or nitrogen and, surprisingly a strong activity of the protonform of the compounds of the invention on certain monomers. The presentinvention also has as an object the use of ionic compounds asphotoinitiators as sources of Brønsted acid which are catalysts for thepolymerization or cross-linking of monomers or prepolymers capable ofcationic reaction, or as catalysts for the modification of polymers.

The process of polymerization or cross-linking of monomers orprepolymers capable of cationic reaction is characterized in that thereis used a compound of the invention as photoinitiator constituting asource of acid catalyzing the polymerization reaction. The compoundsaccording to the invention in which the cation is a group having a bond—N═N⁺, —N═N—, a sulfonium group, an iodonium group, or anarene-ferrocenium cation which is substituted or non-substituted,possibly incorporated in a polymeric network, are particularlypreferred.

The choice of substituents Y, Y_(c) or Q_(s) is made so as to increasethe solubility of said compound in the solvents used for the reaction ofmonomers or prepolymers, and as a function of the desired properties forthe final polymer. For example, the choice of non-substituted alkylradicals gives a solubility in low polar media. The choice of radicalscomprising an oxa group or a sulfone will provide solubility in polarmedia. The radicals including a sulfoxide group, a sulfone group, aphosphine oxide group, a phosphonate group, respectively obtained by theaddition of oxygen on the atoms of sulfur or phosphorus, may give to thepolymer obtained improved properties with respect to adhesion, shine,resistance to oxidation or to UV. The monomers and prepolymers which maybe polymerized or cross-linked with the photoinitiators of the presentinvention are those which may undergo a cationic polymerization.

Among the monomers, monomers which include a cyclic ether function, acyclic thioether function or cyclic amine function, vinyl compounds(more particularly vinyl ethers), oxazolines, lactones and lactames, maybe mentioned.

Among the polymers of the ether or cyclic thioether type, ethyleneoxide, propylene oxide, oxetane, epichlorhydrin, tetrahydrofurane,styrene oxide, cyclohexene oxide, vinylcyclohexene oxide, glycidol,butylene oxide, octylene oxide, glycidyl ethers and esters (for exampleglycidyl methacrylate or acrylate, phenyl glycidyl ether,diglycidylether of bisphenol A or its fluorinated derivatives), cyclicacetals having 4 to 15 carbon atoms (for example dioxolane, 1,3-dioxane,1,3-dioxepane) and spiro-bicyclo dioxolanes, may be mentioned.

Among vinyl compounds, vinyl ethers constitute a very important familyof monomers which are capable of cationic polymerization. By way ofexample, there may be mentioned ethyl vinyl ether, propyl vinyl ether,isobutyl vinyl ether, octadecyl vinyl ether, ethyleneglycol monovinylether, diethyleneglycol divinyl ether, butanediol monovinyl ether,butanediol divinyl ether, hexanediol divinyl ether, ethyleneglycol butylvinyl ether, triethyleneglycol methyl vinyl ether, cyclohexanedimethanolmonovinyl ether, cyclohexanedimethanol divinyl ether, 2-ethylhexyl vinylether, poly-THF-divinyl ether having a molecular weight between 150 and5,000, diethyleneglycol monovinyl ether, trimethylolpropane trivinylether, aminopropyl vinyl ether, 2-diethylaminoethyl vinyl ether.

Other vinyl compounds may include, by way of example,1,1-dialkylethylenes (for example isobutene), vinyl aromatic monomers(for example styrene, α-alkylstyrenes, such as α-methylstyrene,4-vinylanisole, acenaphthene), N-vinyl compounds (for examplesN-vinylpyrolidone or N-vinyl sulfonamides).

Among prepolymers, there may be mentioned compounds in which epoxygroups are carried by an aliphatic chain, an aromatic chain, or aheterocyclic chain, for example glycidic ethers of bisphenol A which areethoxylated by 3 to 15 ethylene oxide units, siloxanes having lateralgroups of the epoxycyclohexene-ethyl type obtained by hydrosilylation ofcopolymers of dialkyl, alkylaryl or diaryl siloxane with methylhydrogenosiloxane in the presence of vinylcyclohexene oxide,condensation products of the sol-gel type obtained from triethoxy ortrimethoxy silapropylcyclohexene oxide, urethanes incorporating thereaction products of butanediol monovinylether and an alcohol of afunctionality higher than or equal to 2 with an aliphatic or aromaticdi- or tri-isocyanate.

The process of polymerization according to the invention consists inmixing at least one monomer or prepolymer capable of cationicpolymerization and at least one ionic compound of the invention, andsubjecting the mixture obtained to actinic or β radiation. Preferably,the reaction mixture is subjected to radiation after having been formedinto a thin layer having a thickness lower than 5 mm, preferably in theform of a thin layer having a thickness lower than or equal to 500 μm.The duration of the reaction depends on the thickness of the sample andthe power of the source at the active λ wavelength. It is defined by thespeed at which it passes in front of the source, which is between 300m/min and 1 cm/min. Layers of the final material having a thicknesshigher than 5 mm may be obtained by repeating many times the operationconsisting in spreading a layer and treating it with radiation.

Generally, the quantity of photoinitiator used is between 0.01 and 15%by weight with respect to the weight of the monomer or prepolymer,preferably between 0.1 and 5% by weight.

An ionic compound of the present invention may be used as photoinitiatorin the absence of solvent, for example when it is intended to polymerizeliquid monomers in which the ionic compound used as photoinitiator issoluble or easily dispersible. This type of utilization is particularlyinteresting, since it enables to overcome the problems associated withsolvents (toxicity, flammability).

An ionic compound of the present invention may also be used asphotoinitiator in the form of a homogeneous solution in a solvent whichis inert towards polymerization, ready to be used and easilydispersible, in particular in the case where the medium to bepolymerized or cross-linked has a high viscosity.

As example of an inert solvent, there may be mentioned volatilesolvents, such as acetone, methyl-ethyl ketone and acetonitrile. Thesesolvents will be used merely to dilute the products to be polymerized orcross-linked (to make them less viscous, especially when dealing with aprepolymer). They will be removed by drying after polymerization orcross-linking. Non-volatile solvents may also be mentioned. Anon-volatile solvent also serves to dilute the products that one wishesto polymerize or cross-link, and to dissolve the ionic compound of theinvention used as photoinitiator, however, it will remain in thematerial formed and will thus act as plasticizing agent. By way ofexample, propylene carbonate, δ-butyrolactone, ether-esters of mono-,di-, tri-ethylene or propylene glycols, ether-alcohols of mono-, di-,tri-ethylene or propylene glycols, plasticizing agents such as esters ofphthalic acid or citric acid, may be mentioned.

According to another embodiment of the invention, there may be used assolvent or diluent a compound which is reactive towards polymerization,which is a compound of low molecular weight and of low viscosity whichwill simultaneously act as polymerization monomer and solvent or diluentfor more viscous polymers or prepolymers used in combination. After thereaction, these monomers having been used as solvent will be part of themacromolecular network finally obtained, their integration being widerwhen dealing with bi-functional monomers. The material obtained afterirradiation is now free of products having a low molecular weight and asubstantial vapour tension, or capable of contaminating objects withwhich the polymer is in contact. By way of example, a reactive solventmay be selected from mono and divinyl ethers of mono-, di-, tri-,tetra-ethylene and propylene glycols, N-methylpyrolidone,2-propenylether of propylene carbonate commercially available forexample under the commercial designation PEPC from ISP, New Jersey,United States.

To irradiate the reaction mixture, the irradiation may be selected fromultraviolet radiation, visible radiation, X-rays, δ rays and βradiation. When ultraviolet light is used as actinic radiation, it maybe advantageous to add to the photoinitiators of the inventionphotosensitizers intended to provide an efficient photolysis withwavelengths which are less energetic than those corresponding to themaximum of absorption of the photoinitiator, such as those produced byindustrial devices, (I≈300 nm for mercury vapour lamps in particular).Such additives are known, and by way of non-limiting example, there maybe mentioned anthracene, diphenyl-9,10-anthracene, perylene,phenothiazine, tetracene, xanthone, thioxanthone, acetophenone,benzophenone, 1,3,5-triaryl-2-pyrazolines and derivatives thereof, inparticular derivatives which are substituted on the aromatic nuclei byalkyl, oxa- or aza-alkyl radicals, enabling inter alia to change theabsorption wavelength. Isopropylthioxantone is an example of preferredphotosensitizer when an iodonium salt according to the invention is usedas photoinitiator.

Among the different types of radiation mentioned, ultraviolet radiationis particularly preferred. On the one hand, it is more convenient to usethan the other radiations mentioned. On the other hand, photoinitiatorsare in general directly sensitive towards UV rays and photosensitizersare more efficient when the difference of energy (δλ) is lower.

The ionic compounds of the invention may also be used in associationwith free radical initiators produced thermally or by action of actinicradiation. It is also possible to polymerize or cross-link mixtures ofmonomers or polymers containing functions in which the types ofpolymerization are different, for example, monomers or prepolymers whichpolymerize by free radical and monomers or prepolymers which polymerizeby cationic polymerization. This possibility is particularlyadvantageous for producing interpenetrated networks having physicalproperties which are different from those which would be obtained by asimple mixture of polymers originating from corresponding monomers.Vinyl ethers are not or are very little active by free radicalinitiation. It is therefore possible, in a reaction mixture containing aphotoinitiator according to the invention, a free radical initiator, atleast one monomer of the vinyl ether type and at least one monomercomprising non-activated double bonds such as those of the allyl groups,to carry out a separate polymerization for each type of monomer. On theother hand, it is known that monomers which are lacking in electrons,such as esters or amides of fumaric acid, maleic acid, acrylic ormethacrylic acid, itaconic acid, acrylonitrile, methacrylonitrile,maleimide and derivatives thereof, form in the presence of vinyl etherswhich are enriched in electrons, complexes of transfer of charge givingalternated polymers 1:1 by free radical initiation. An initial excess ofvinyl monomers with respect to this stoichiometry enables to preservepolymerizable functions by pure cationic initiation. The start of theactivity of a mixture of free radical initiator and cationic initiatoraccording to the invention may be carried simultaneously for the tworeactants in the case for example of insolation by actinic radiation ofa wavelength for which the photoinitiators of the invention and theselected radical initiators are active, for example at I=250 nm. By wayof example, the following commercial products: Irgacure 184®, Irgacure651®, Irgacure 261®, Quantacure DMB®, Quantacure ITX® may be mentionedas initiators.

It may also be advantageous to use the two types of polymerization in asequential manner, to first form prepolymers which are easy to shape andin which hardening, adhesion, solubility as well as degree ofcross-linking may be modified by initiating the activity of the cationicinitiator. For example, a mixture of a thermo-dissociable radicalinitiator and a cationic photoinitiator according to the inventionenables to provide sequential polymerizations or cross-linking, firstunder the action of heat, then under the action of actinic radiation.Similarly, if a free radical initiator and a cationic photoinitiatoraccording to the invention are selected, the first being photosensitiveat longer wavelengths than the one initiating the photoinitiatoraccording to he invention, there is obtained a cross-linking in twocontrollable steps. Free radical initiators may for example be Irgacure®651 enabling to initiate free radical polymerizations at wavelength of365 nm.

The invention also has as an object the use of ionic compounds of theinvention for chemical amplification reactions of photoresists in thefield of microlithography. During such use, a film of a materialcomprising a polymer and an ionic compound of the invention is subjectto irradiation. The irradiation causes the formation of the acid byreplacement of the cation M with a proton, which catalyzes thedecomposition or transformation of the polymer. After decomposition ortransformation of the polymer on the parts of the film which have beenirradiated, the monomers formed or the polymer which has been convertedare removed and what remains is an image of the unexposed parts. Forthis particular application, it is advantageous to use a compound of theinvention which is in the form of a polymer consisting essentially ofstyrenyl recuriing units carrying a pentacyclic anionic group or a groupderived from tetrazapentalene. These compounds enable to obtain afterphotolysis products which are not volatile, and therefore notodoriferous when dealing with sulfides. Among the polymers which maythus be modified in the presence of a compound of the invention, theremay for example be cited polymers containing ester units ortertiaryalkyl arylether units, for example poly(phthaldehydes), polymersof bisphenol A and a diacid, polytertiobutoxycarbonyl oxystyrene,polytertiobutoxy-a-methyl styrene,polyditertiobutylfiumarate-co-allyltrimethyl-silane and polyacrylates ofa tertiary alcohol, in particular tertiobutyl polyacrylate. Otherpolymers are described in J. V. Crivello et al, Chemistry of Materials8, 376-381, (1996).

The ionic compounds of the present invention, which have an elevatedthermal stability, give numerous advantages with respect to known saltsof the prior art. They have speeds of initiation and propagation whichare comparable or higher than those obtained with coordination anions ofthe type PF₆—, AsF₆— and especially SbF₆—.

In the compounds of the present invention, the pairs of ions have a veryhigh dissociation, which enables the expression of intrinsic catalyticproperties of the cation M^(m+), in which the active orbits are easilyexposed to substrates of the reaction, especially in different media.Most of the important reactions of organic chemistry may thus be carriedout under relatively easy conditions, with excellent yields and thepossibility of separating the catalyst from the reaction mixture. Thedemonstration of asymmetric induction by the use of an ionic compoundaccording to the invention which carries a chiral group is particularlyimportant in view of its generality and its ease of operation. Thepresent invention consequently has as another object the use ofcompounds of the invention as catalysts in Friedel-Crafts reactions,Diels-Alder reactions, aldolization reactions, additions of Michael,reactions of allylation, reactions of pinacolic coupling, reaction ofglycosilation, reaction of openings of the cycle of oxetanes, reactionsof metathesis of alkenes, polymerizations of the Ziegler-Natta type,polymerizations of the metathesis type by cycle opening andpolymerizations of the metathesis type of acyclic dienes. The preferredionic compounds of the invention for utilization as catalyst for theabove reactions are those in which the cation is selected from lithium,magnesium, copper, zinc, tin, trivalent metals, including rare earths,platinoids, and their organometallic couples, in particularmetallocenes.

The compounds of the invention may also be used as solvent to carry outchemical, photochemical, electrochemical, photoelectrochemicalreactions. For this particular use, the ionic compounds in which thecation is an imidazolium, triazolium, pyridinium or4-dimethylamino-pyridinium, are preferred, said cation possibly carryinga substituent on the carbon atoms of the cycle. Among the compounds usedin liquid form, those having a melting point lower than 150° C., moreparticularly lower than 100° C., are particularly preferred. Theinventors have also found that the anionic charge carried by thepentacyclic group or the group derived from tetrazapentalene exerts astabilizing effect on electronic conductors of the conjugated polymertype, and that use of a compound in which one of the substituents Y,Y_(c) or Q_(s) comprises a long alkyl chain enables to make thesepolymers soluble in the usual organic solvents even in doped state.Grafting of these charges on the polymer itself gives polymers in whichthe global charge is cationic, which are soluble in organic solvents andhave, in addition to their stability, properties of anticorrosiontowards metals, aluminum and ferrous metals. It is also an object of thepresent invention to provide electronically conductive materialcomprising an ionic compound of the present invention in which thecationic part is a polycation constituted of a doped “p” conjugatedpolymer. The preferred ionic compounds for this application are those inwhich one of the substituents Q or Q_(s) contains at least one alkylchain having 6 to 20 carbon atoms. Additionally, the compounds in whichY or Y_(c) represents an aromatic nucleus carrying an alkyl radical maybe mentioned.

The coloring materials of cationic type (cyanines) are used more andmore frequently as sensitizers of photographic films, for storingoptical information (optical disks accessible in writing), for lasers.The tendency of these conjugated molecules to pile over one another whenthey are in solid phase limits their utilization, because of thevariation of the optical properties with respect to the isolatedmolecule. The use of ionic compounds of the invention for manufacturingcationic coloring materials including counter ions, possibly bound tothis same molecule, correspond to functions of the invention, enables toreduce phenomenon of aggregation, including in solid polymer matricesand to stabilize these coloring materials. It is another object of thepresent invention to provide a composition of cationic coloringmaterial, characterized in that it contains an ionic compound accordingto the invention. The particularly preferred ionic compounds for thisapplication are those in which the negative charge(s) of the pentacyclicanionic group or a group derived from tetrazapentalene are either fixedto the molecule of the coloring material, or they constitute thecounter-ion of the positive charges of the coloring material.

The compounds of the present invention may be obtained by processes ofsynthesis well known to those skilled in the art. Among these processes,some consist in building the cycle, others consist in modifying existingcycles.

By way of example, a pentacyclic compound in which two groups X_(i) aregroups —C(CN)═ and a group X_(i) is a group —S(═O)(CF₃)— may be obtainedby reacting diaminomaleonitrile and sodium triflinate in the presence ofa dehydrating agent, according to the first of the following reactionschemes.

A pentacyclic compound in which two groups X_(i) are groups —C(CN)═ anda group X_(i) is a group —P(CF₃)₂— may be obtained by reacting4,5-dicyano-1,3,2-diazaphospholate with a suitable trifluoromethylationagent, according to the second reaction scheme which follows.

Other processes of preparation are described more in detail in thefollowing examples, which illustrate compounds of the invention andtheir uses. The present invention is however not limited to thesespecific examples.

EXAMPLE 1

To 136.11 g (1 mole) of aminoguanidine bicarbonate H₂NNHC(═NH)NH₂.H₂CO₃in 500 ml of toluene under stirring, there is added 119.73 g (1.05moles) of trifluoroacetic acid CF₃CO₂H. After adding the acid and whenescape of CO₂ has ceased, an azeotropic distillation was carried out bymeans of a Dean-Stark. After 24 hours, 54.5 ml (stoichiometry 55 ml) ofwater was recovered in the Dean-Stark container. After cooling thesolution in toluene, while crystals appeared which have been recoveredby filtration on a fritted glass of porosity N° 3. After drying, 139.9 g(92% yield) of 2-amino-5-trifluoromethyl-1,3,4-triazole, having a puritydetermined by a proton and fluorine RMN higher than 99%.

The corresponding potassium salts were prepared by reacting2-amino-5-trifluoromethyl-1,3,4-triazole with potassium carbonate K₂CO₃in water (20% in excess). After evaporating water and drying, theproduct obtained was reclaimed in acetonitrile, and the excess ofcarbonate was removed by filtration. After evaporation of acetonitrileand drying, the potassium salt of2-amino-5-trifluoromethyl-1,3,4-triazole was obtained in quantitativeyield.

30.42 g (200 mmoles) of the potassium salt of2-amino-5-trifluoromethyl-1,3,4-triazole (obtained according to theprocess described in Example 1) were dissolved in 20 ml of a 1 Msolution of hydrochloric acid at 0° C. To the solution under stirring,13.8 g (200 mmoles) of potassium nitrite NaNO₂ were added by portions. Aprecipitate of diazo-trifluoromethyltriazole is immediately formed.After 15 min, 9.8 g (200 mmoles) of sodium cyanide NaCN, 35.8 g (400mmoles) of copper(I) cyanide CuCN and 2 ml of dioxane were added. Anescape of nitrogen was then noted. After one night, 13.82 g (100 mmoles)of potassium carbonate were added to permit a precipitation of coppercarbonate. After filtration, the solution was evaporated, the residuewas dried, and it was reclaimed in 100 ml of methyl formate. Afterfiltration, evaporation and drying, the residue was reclaimed in 200 mlof a 1 M solution of hydrochloric acid, and was extracted with twofractions of 50 ml of ether. After drying the organic phase withmagnesium sulfate and evaporation of ether, the product obtained wassublimated under secondary vacuum at 40° C. After 48 hours, 9.89 g (61%yield) of 2-cyano-5-trifluoromethyl-1,3,4-triazole were recovered on acold finger, with a purity determined by a proton and fluorine RMNhigher than 99%.

The corresponding potassium salt was prepared by treating2-cyano-5-trifluoromethyl-1,3,4-triazole by a process similar to the onedescribed above for obtaining the potassium salt of2-amino-5-trifluoromethyl-1,3,4-triazole.

The salts of sodium and lithium were obtained by a similar process, byreplacing potassium carbonate respectively with sodium carbonate andlithium carbonate.

These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly(ethyleneoxide). In this latter solvent, at a concentration of O/Li of 14/1, thelithium salt has a ionic conductivity higher than 10⁻⁴ S.cm⁻¹ at atemperature of 60° C.

EXAMPLE 2

By a process similar to the one described in Example 1, but by replacingtrifluoroacetic acid with 5-ene-2,2-difluoroheptanoic acid, the compound2-(4-ene-1,1-difluorobutyl)-5-cyano-1,3,4-triazole was prepared, with apurity determined by a proton and fluorine RMN higher than 99%.

Potassium, sodium and lithium salts were obtained by treating triazolewith corresponding carbonates.

EXAMPLE 3

19.02 g (100 mmoles) of the potassium salt of2-amino-5-trifluoromethyl-1,3,4-triazole prepared according to theprocess of Example 1 were dissolved in 25 ml of acetonitrile at −20° C.Then, 11.68 g (100 mmoles) of nitrosonium tetrafluoroborate NOBF₄ wereadded by portions. After 1 hour under stirring, the reaction mixture wasfiltered to remove the precipitate of potassium tetraborate KBF₄. Then,there was added 17.22 g (100 mmoles) of CF₃SO₂K (commercially availablefrom Parish) in solution in 25 ml of DMF and a trace of copper ascatalyst. Formation of fine bubbles of nitrogen in the solution wasnoted. After 48 hours under stirring, the solution was evaporated andthe residue was recrystallized in 50 ml of water to which 7.46 g (100mmoles) of anhydrous potassium chloride KCl were added. After filteringand drying, 20.83 g (72% yield) of the potassium salt of2-trifluoromethanesulfonyl-5-trifluoromethyl-1,3,4-hiazole wereobtained, with a purity determined by a proton and fluorine RMN higherthan 99%.

The lithium salt was obtained by ionic exchange in THF with lithiumchloride. The acid was obtained by extraction with ether of an aqueoussolution of the potassium salt acidified with hydrochloric acid.

The scandium salt was obtained by treating 10 mmoles of said acid, insolution in 10 ml of water, with 1.67 mmoles of scandium acetate. Afterstirring overnight, water was evaporated and the lanthanum salt of thiscompound was recovered in quantitative yield after drying.

EXAMPLE 4

11.81 g (100 mmoles) of 4,5-dicyanoimidazole and 10.12 g (100 mmoles) oftriethylamine were placed in solution in 100 ml of tetrahydrofurane(THF). After bringing the solution to 0° C., there is slowly added,under argon, 14.06 g of benzoyl chloride. After 6 hours under stirring,the reaction mixture was filtered to remove the precipitate oftriethylammonium chloride. Then, 30.21 g (100 mmoles) ofperfluorobutanesulfonyl fluoride C₄F₉SO₂F and 11.22 g (100 mmoles) of1,4-diazabicyclo[2.2.2.]octane (DABCO) were added to the solution. After72 hours under stirring, the reaction mixture was filtered to remove theprecipitate of DABCO hydrochloride, and the solvent was evaporated. Theresidue was then reclaimed in 100 ml of a 2 M solution of potassiumhydroxide and the solution was heated to reflux during 4 hours. Aftercooling the solution, a precipitate appeared which was recovered byfiltration. There is thus obtained 31.56 g (72% yield) of the potassiumsalt of 2-perfluorobutanesulfonyl-4,5-dicyanoimidazole, with a puritydetermined by a proton and fluorine RMN higher than 99%.

The corresponding acid was obtained by ether extraction of an aqueoussolution acidified with the potassium salt. The lithium salt wasobtained by treating this acid with lithium carbonate Li₂CO₃.

EXAMPLE 5

In 50 ml of water, 11.81 g (100 mmoles) of 4,5-dicyanoimidazole werereacted with 5.3 g (50 mmoles) of anhydrous sodium carbonate Na₂CO₃.After 15 min under stirring, the solution was brought to 0° C. and 11 g(100 mmoles) of the sodium salt of dichloroisocyanuric acid was added.After one night, the solution was centrifuged in order to remove thesodium salt of isocyanuric acid which was formed during the reaction.After adding 14.91 g (200 mmoles) of anhydrous potassium chloride, theprecipitate obtained was recrystallized. After filtration and drying,11.88 g (62% yield) of the potassium salt of2-chloro-4,5-dicyanoimidazole was recovered, with a purity determined bya proton and fluorine RMN higher than 98%.

The lithium salt was obtained by ionic exchange in THF with lithiumchloride.

EXAMPLE 6

To 8.89 g (40 mmoles) of the potassium salt of2-(4-ene-1,1-difluoropropane)-5-cyano-1,3,4-triazole, obtained by aprocess as described in Example 2, in 100 ml of water, there is added6.9 g (40 mmoles) of 3-chioroperoxybenzoic acid, obtained according tothe process described by Scwartz & Blumbergs (J. Org. Chem., (1964),1976). After one hour under strong stirring, the solvent was removed,and the residue was recrystallized in 10 ml of ethanol. After filtrationand drying, the potassium salt of2-(3,4-epoxy-1,1-difluorobutane)-5-cyano-1,3,4-triazole was recovered,with a purity characterized by a proton and fluorine RMN higher than98%.

The lithium salt was obtained by treating the potassium salt inanhydrous tetrahydrofurane with a stoichiometric quantity of anhydrouslithium chloride, filtration of the reaction mixture, evaporation of thesolvent and drying under vacuum.

The homopolymer of the potassium salt of2-(3,4-epoxy-1,1-difluorobutane)-5-cyano-1,3,4-triazole was prepared bypolymerization in tetrahydrofurane anionically initiated with potassiumtert-butoxide, and the polysalt of lithium was obtained by ionicexchange in THF with anhydrous lithium chloride. The polysalt of lithiumhas a conductivity in gelled medium (21% by weight of polyacrylonitrile,38% ethylene carbonate, 33% propylene carbonate, 8% homopolymer) of 1.2×10⁻³ S.cm⁻³ 1 at 30° C. The cationic transport number in thiselectrolyte is 0.92. Moreover, this polysalt is soluble in most of theusual organic solvents (tetrahydrofurane, acetonitrile,dimethylformamide, ethyl acetate, glymes, . . . ) and in aproticsolvating polymers.

EXAMPLE 7

In a glove box under argon, to a solution of 16.02 g (200 mmoles) ofsuccinonitrile NCCH₂CH₂CN and 41.61 g (200 mmoles) ofhexafluoroacetylketone CF₃COCH₂COCF₃ in 200 ml of anhydrous THF, thereis added by portions 2.38 of lithium hydride (300 mmoles). After 48hours, the reaction mixture was filtered, and the solvent wasevaporated. The residue was recrystallized in 100 ml of water to which14.91 g (200 mmoles) of anhydrous potassium chloride were added. Afterfiltration and drying, 44.26 g (76% yield) of the potassium salt2,5-trifluoromethyl-3,4-dicyano-cyclopentadiene were obtained, with apurity determined by a proton and fluorine PMN higher than 98%.

By a similar process, the potassium salt of the following compounds wereprepared:

2-t-butyl-5-heptafluoropropyl-3,4-dicyano-cyclopentadiene (I) from1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione;

2-trifluoromethyl-5-heptafluoropropyl-3,4-dicyano-cyclopentadiene (II)from 1,1,1,5,5,6,6,7,7,7-decafluoro-2,4-heptanedione;

2-(2-furyl)-5-trifluoromethyl-3,4-dicyano-cyclopentadiene (III), from4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione;

2-(2-thienyl)-5-trifluoromethyl-3,4-dicyano-cyclopentadiene (IV), from1-(2-thenoyl)-3,3,3-trifluoroacetone.

These salts may easily be modified by reactions of nucelophilicsubstitution on the carbon carrying no substituent.

The acids were obtained by ether extraction of aqueous solutions ofpotassium salts which are acidified with hydrochloric acid.

EXAMPLE 8

3.03 g (10 mmoles) of stearic acid chloride C₁₇H₃₅COCl and 2.9 g of2,5-trifluoromethyl-3,4-dicyano-cyclopentadiene (prepared according tothe process of Example 7) were reacted in 20 ml of THF in the presenceof 5 ml of pyridine. After 24 hours under stirring, the solution wasfiltered to remove the precipitate of potassium chloride, and contactedwith 500 mg of lithium carbonate Li₂CO₃. The mixture was stirred during24 hours, the excess of carbonate was removed by centrifugation, and thesolvent was evaporated. 5.12 g of the lithium salt of1-stearyl-2,5-trifluoromethyl-3,4-dicyano-cyclopentadiene were obtained,with a purity characterized by a proton and carbon RMN higher than 97%.

This salt has noted tensio-active properties, including in solvents andaprotic solvating polymers.

EXAMPLE 9

324 mg of 4-(dimethylamino)azobenzene-4′-sulfonyl chloride (1 mmole)were reacted with 290 mg of the potassium salt of2,5-trifluoromethyl-3,4-dicyano-cyclopentadiene (1 mmole), in 10 ml ofTHF, in the presence of 5 μl of triethylamine. After 24 hours understirring, the potassium chloride precipitate was removed and, afterevaporation, the triethylammonium salt was obtained which was suspendedin 5 ml of water containing in solution 350 mg of tetrabutylammoniumbromide. The mixture was stirred during 24 hours. There is obtained apowder of orange color, with a purity characterized by a proton andcarbon RMN higher than 98%. This powder is soluble in most of theorganic solvents and corresponds to the following formula.

The compound may be used a pH indicator in non-aqueous medium(transition yellow-orange-red-violet in the pH zone 1-4).

EXAMPLE 10

501 mg (2 mmoles) of 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylicacid (Trolox®) were suspended in 10 ml of ethyl acetate and 1 ml ofpyridine. To this mixture, 580 mg (2 mmoles) of the potassium salt of2,5-trifluoromethyl-3,4-dicyano-cyclopentadiene and 313 μl (2 mmoles) of1,3-diisopropylcarbodiimide were added. After 24 hours, thediisopropylurea precipitate was filtered and the volume of the solutionwas reduced to 2 ml by means of a rotary evaporator. 20 ml of hexanewere added and the mixture was cooled to −10° C. A white precipitate wascollected by filtration. Its analysis corresponds to C₂₃H₁₇N₂O₃KF₆. Ithas antioxidizing properties, in particular for polymers.

The same is true with respect to derivatives of other cations, includingorganic cations such as tetraalkylamomoniums.

EXAMPLE 11

2.8 (10 mmoles) of 4,4′-azobis(4-cyanovaleric) were suspended in 20 mlof methyl formate and 5 ml of pyridine. 5.16 g (20 moles) of lithium2,5-trifluoromethyl-3,4-dicyano-cyclopentadiene and 4.16 g (20 mmoles)of dicyclohexylcarbodiimide were added. The mixture was kept undermagnetic stirring at 0° C. during 48 hours. The precipitate ofdicyclohexylurea was removed by centrifugation and the solution wasevaporated at room temperature. There is obtained a crystalline solidwhich is soluble in particular in acetone, acetonitrile, ethyl acetate,tetrahydrofurane. This compound may be used as a free radical initiatorto initiate reactions of polymerization or of cross-linking even as lowas 60° C.

EXAMPLE 12

In a Parr chemical reactor, there is introduced 200 ml of anhydrousacetonitrile and 13 g (200 mmoles) of sodium nitride NaN₃. After closingthe reactor, the latter was flushed with nitrogen, and 25 g (154 mmoles,commercially available from Aldrich) of hexafluorobutyne CF₃C≡CF₃ wereintroduced. After 24 hours under stirring, the reaction mixture wasfiltered and the solvent was evaporated. The residue was reclaimed in154 ml (154 mmoles) of a 1 M solution of hydrochloric acid, and wasextracted with two fractions of 50 ml ether. After drying the organicphase with magnesium sulfate and evaporating ether, there is obtained aproduct which was sublimated under vacuum at 40° C. 27.16 g (86% yield)of 4,5-trifluoromethyl-1H-1,2,3-triazole were recovered after 24 hourson a cold finger, with a purity determined by a proton and fluorine RMNhigher than 99%.

The lithium salt was obtained by treating the acid with lithiumcarbonate in water.

By a similar process, the following salts of lithium were prepared;

4-trifluoromethyl-5-cyano-1H-1,2,3-triazole (I) from 1-cyano-3,3,3-trifluoropropyne CF₃ C≡CCN;

4-pentafluoroethyl-5-cyano-1H-1,2,3-triazole (II), from1-cyano-4,4,4,3,3-pentafluorobutyne C₂F₅C≡CCN;

4-heptafluoropropyl-5-cyano-1H-1,2,3-triazole (III), from1-cyano-5,5,5,4,4,3,3-heptafluoroheptyne C₃F₇C≡CCN.

The three alkynes used were obtained according to the proceduredescribed by Huang, Shen, Ding, Zheng (Tetrahedron Lett., (1981), 22,5283).

These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly(ethyleneoxide). The concentrated solutions of these salts in acetone may be usedas catalyst in Diels-Alder reactions.

EXAMPLE 13

13 g (200 mmoles) of sodium nitride NaN₃ and 23.29 g (100 mmoles) of2,3-dichloro-hexafluoro-2-butene CF₃CCl═CClCF₃ in 50 ml of DMF werereacted in the presence of 13.09 g (200 mmoles) of zinc. After 72 hoursunder stirring, the reaction mixture was filtered and the solvent wasevaporated. The residue was reclaimed in 154 ml (154 mmoles) of a 1 Msolution of hydrochloric acid, and it was extracted with two fractionsof 50 ml ether. After drying the organic phase with magnesium sulfateand evaporation of ether, there is obtained a product which wassublimated under vacuum at 40° C. After 24 hours, 14.76 g (72% yield) of4,5-trifluoromethyl-1H-1,2,3-triazole were recovered on a cold finger,with a purity determined by a proton and fluorine RMN higher than 99%.

In 20 ml of ether, 4.1 g of this compound (20 mmoles) and 1.38 g of1,2,3-triazole (20 mmoles) were dissolved. There is immediately formed aprecipitate which was recovered by filtration and dried. The followingsalt was obtained:

A molar mixture of three 1,2,3-triazole for one triazolium salt wascrushed in a mortar placed in a glove box. There is obtained a liquid inthe mortar. This molten salt has a high protonic conductivity higherthan 10⁻³ S.cm⁻¹ at 30° C. It may be used to prepare a polymerelectrolyte, which is an anhydrous proton conductor, by addingpoly(ethylene oxide), preferably of high molecular weight or which couldlater on be cross-linked, to the molten salt without harming itsconductivity. These polymer electrolytes are particularly interestingfor providing systems of modulation of light such as electrochromeglazings including electrochrome systems with coloring materials.

A polymer electrolyte consisting of 80% by weight of said molten saltand 20% by weight of poly(ethylene oxide) of molecular weight 5×10⁶ wasused to prepare a membrane which is optically transparent in the visiblerange and has a good mechanical behaviour. Then, an electrochrome systemwas prepared in a glove box by utilizing this membrane enclosed betweena first electrode consisting of the deposit of a layer of hydrogenatediridium oxide H_(x)IrO₂ on a glass plate and a conductive sub-layer oftin oxide, and a second electrode consisting of a layer of tungstentrioxide WO₃ and a conductive sub-layer of tin oxide. This electrochromeenabled a variation of optical absorption between 80% (discolored state)and 30% (colored state) and good performances in cycling (more than20,000 cycles).

EXAMPLE 14

11.81 g (100 mmoles) of 4,5-dicyanoimidazole and 10.12 g (100 mmoles) oftriethylamine were placed in solution in 100 ml of THF. After bringingthis solution to 0° C., there is slowly added, under argon, 14.06 g ofbenzoyl chloride. After 6 hours under stirring, the reaction mixture wasfiltered to remove the triethylammonium chloride precipitate. Then,there is added to the solution 16.85 g (100 mmoles) oftrifluoromethanesulfonyl chloride and 11.22 g (100 mmoles) of DABCO.After 72 hours under stirring, the reaction mixture was filtered toremove the precipitate of DABCO hydrochloride, and the solvent wasevaporated. The residue was then reclaimed in 10 ml of a 2 M solution ofpotassium hydroxide and the solution was heated to reflux during 4hours. After cooling the solution, a precipitate appeared which wasrecovered by filtration. There is thus obtained 21 g of potassium2-trifluoromethanesulfonyl-4,5-dicyanoimidazole, with a puritydetermined by a proton and fluorine RMN higher than 99%.

By a similar process, but by replacing trifluoromethanesulfonyl chloridewith 2,2,2-trifluoroethyl trifluoroacetate CF₃CO₂CH₂CF₃, there isobtained potassium 2-trifluoroacetyl-4,5-dicyanoimidazole (yield 69%),with a purity determined by a proton and fluorine RMN higher than 99%.

By a similar process, but by replacing trifluoromethanesulfonyl chloridewith trifluoroethanesulfonyl chloride CF₃CH₂SO₂Cl, there is obtainedpotassium 2-trifluoroethanesulfonyl-4,5-dicyanoimidazole (yield 73%),with a purity determined by a proton and fluorine RMN higher than 99%.

By a similar process, but by replacing trifluoromethanesulfonyl chloridewith sulfamoyl chloride (CH₃)2NSO₂Cl, there is obtained potassium2-dimethylaminosulfonyl-4,5-dicyanoimidazole (yield 73%), with a puritydetermined by a proton and fluorine RMN higher than 99%.

EXAMPLE 15

By operating in a glove box under argon, to 24.15 g (100 mmoles) ofdi-2-ethylhexylamine in 100 ml of THF at −20° C., there is added byportions 32 ml is of butyllithium 2 M in cyclohexane (100 mmoles). Afterone hour, 11.85 g (100 mmoles) of chlorosulfonyl fluoride FSO₂Cl wereadded. The reaction was continued for 4 hours at −20° C., and during 24hours at room temperature. The process as in Example 14 was repeated byreplacing trifluoromethanesulfonyl chloride withdi-2-ethylhexylaminosulfonyl chloride in solution in THF. There isobtained the following compound:

The potassium salt was obtained by treating the lithium salt in aminimum amount of water with potassium fluoride KF. After filtration,evaporation and drying, the potassium salt was recovered in quantitativeyield.

These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers.

EXAMPLE 16

To 13.83 g (100 mmoles) of 1-decyne C₈H₁₇C≡CH (commercially availablefrom Aldrich) in 100 ml of anhydrous tetrahydrofurane at −20° C., thereis added under argon during 30 min, 33.4 ml of a 3 M solution ofmethylmagnesium chloride (100 mmoles). After 1 hour at −20° C., there isslowly added 30.21 g (100 mmoles) of perfluorobutanesulfonyl fluorideand, after 2 hours at −20° C., there is added by small portions during aperiod of 1 hour, 6.5 g (100 mmoles) of sodium nitride NaN₃. Thereaction was continued during 3 hours at −20° C. and during 24 hours atroom temperature. The reaction mixture was then stirred during 24 hourswith 4.24 g (100 mmoles) of anhydrous lithium chloride LiCl. Aftercentrifugation and filtration of the reaction mixture on a fritted glassof porosity N° 5, there is recovered after drying under vacuum 45.52 g(97% yield) of the lithium salt of3-decyne-4-trifluoromethanesulfonyl-1,2,3-triazole, with a puritycharacterized by a proton and fluorine RMN>96%.

Microanalysis has given: H, 3.77 (3,65); Li, 1.46 (1.48); C, 36.45(35.83); N, 8.85 (8.95); F, 35.99 (36.43); S, 6.75 (6.83).

This salt is useful as surfactant. For example, at a concentration aslow as 0.1 g/l in water, the surface tension is decreased to a valuelower than 25 mN/m.

EXAMPLE 17

In a glove box under argon, to a solution of 1.6 g (20 mmoles) ofsuccinonitrile NCCH₂CH₂CN and 4.52 g (20 mmoles) of1,1,1,3,5,5,5-heptafluoropentane-2,4-dione CF₃COCH(F)COCF₃ in 20 ml ofanhydrous THF, there is added by portions 238 mg (30 mmoles) of lithiumhydride. After 48 hours, the reaction mixture was filtered, and thesolvent was evaporated. The residue was recrystallized in 10 ml of waterto which 1.49 g (200 mmoles) of anhydrous potassium chloride has beenadded. After filtration and drying, 4.38 g (71% yield) of the potassiumsalt of 1-fluoro-2,5-trifluoromethyl-3,4-dicyano-cyclopentadiene wereobtained, with a purity determined by a proton and fluorine RMN higherthan 98%.

EXAMPLE 18

A solution of 74.08 g (1 mole) of acetylhydrazide CH₃CONH₂ and 87.12 g(1 mole) of ethyl acetamidate CH₃C(═NH)OC₂H₅ in 500 ml of ethanol wasrefluxed during 4 hours. After evaporation of the solvent, theacylamidrazone obtained CH₃C(=NNHCOCH₃)NH₂ was melted under vacuum at110° C. After 24 hours, the product obtained was recrystallized inbenzene. After filtration and drying, 59.24 g (61% yield) of3,5-dimethyl-1H-1,2,4-triazole were recovered, with a purity determinedby a proton and carbon RMN higher than 99%.

48.56 g (500 mmoles) of this compound, in solution in 400 ml of carbontetrachloride CCl₄, were then chlorinated, by passing a flow of Cl₂ inthe solution. After 24 hours, the solvent was evaporated, the productdried, and it was confined in a chemical reactor designed to carry outchemical reactions in anhydrous hydrogen fluoride HF. After flushing thereactor with argon, 500 g of anhydrous hydrogen fluoride (commerciallyavailable from Spolchemie, Czech Republic) were introduced. After 72hours under stirring, hydrogen fluoride was evaporated and the productwhich was recovered in the reactor was sublimated under vacuum at 40° C.There is then obtained 84 g (82% yield) of3,5-trifluoromethyl-1H-1,2,4-triazole, with a purity characterized by aproton and fluorine RMN higher than 99%.

The scandium salt was prepared by treating 10 mmoles of this compound,in solution in 10 ml of water, with 1.67 mmoles of scandium acetate.After stirring overnight, water was evaporated and the scandium salt wasrecovered in quantitative yield after drying.

EXAMPLE 19

A solution containing 16.96 (40 mmoles) of lithium1-(4-styrenesulfonyl)-2,5-trifluoromethyl-3,4-dicyanoimidazole-cyclopentadieneprepared as in Example 8 by replacing stearic acid chloride with4-styrene-sulfonyl chloride (commercially available from Monomers &Polymers Dajac Laboratories), 3.18 g of acrylonitrile (60 mmoles) and100 mg of 1,1 ′-azobis(cyclohexanecarbonitrile) in 100 ml of anhydrousTHF was degassed with a flow of dry argon. The reaction mixture was thenheated at 60° C. during 48 hours under argon to copolymerizeacrylonitrile with the styrene derivative. After cooling, the solutionwas concentrated, and the polymer was recovered by reprecipitation inether. After filtration and drying, the following polymer was obtained:

This polymer is useful for gelled polymer electrolytes with fixedanions. It constitutes a matrix in the form of a gel and it behaves as apolyelectrolyte.

An electrochemical generator was mounted by superposing the followinglayers:

a current collector of stainless steel with a thickness of 2 mm;

a composite anode consisting of carbon coke (80% by volume) mixed withsaid copolymer as binder (20% by volume);

said gelled copolymer as electrolyte;

a composite cathode consisting of carbon black (6% by volume), LiCoO₂(75% by volume) and said gelled copolymer (20% by volume);

an current collector similar to the above mentioned collector.

This generator enabled to carry out 1,000 cycles of charge/dischargebetween 3 and 4.2 V by keeping a capacity higher than 80% of thecapacity during the first cycle, when cycling at 25° C. It has very goodperformances during calls for power due to the use of fixed anions.Utilization of fixed anions also enable to improve the evolution of theresistance at the interface.

EXAMPLE 20

By a process similar to the one used in Example 19, a copolymer ofacrylonitrile (97% molar) and the lithium salt of1-(4-styrenesulfonyl)-2,5-trifluoromethyl-3,4-dicyanoimidazole-cyclopentadiene(3% molar) was synthesized.

This copolymer in the form of an alkali metal or ammonium salt hasantistatic properties and may therefore advantageously replaceacrylonitrile copolymers which to this day are widely used in the formof fiber for textiles, but which presents no antistatic properties.Moreover, spinning of this copolymer is easier than that of non-modifiedPAN.

This copolymer has very good interactions with cationic coloringmaterials such as methylene blue, which makes it a material of interestfor colored textile fibers. The stability of the color is clearlyimproved as compared to the known copolymer of acrylonitrile andmethallylsulfonate.

EXAMPLE 21

To 3.4 g (10 mmoles) of2-t-butyl-5-heptafluoropropyl-3,4-dicyanocyclopentadiene, obtained inExample 7, and 831 mg (5 mmoles) of 1,1,3,3-tetramethoxypropane in 10 mlof water under stirring, there is added two drops of concentratedsulfuric acid. After 4 hours under stirring, 600 mg of anhydrous lithiumcarbonate Li₂CO₃ were added and, after 15 min, there is added 3.22 g (10mmoles) of tetrabutylammonium bromide (C₄H₉)4NBr. By extraction withdichloromethane, the following compound was recovered:

This anionic coloring material of the cyanine family, which is anabsorbent in the visible range, is soluble in low polar solvents such asdichloromethane or methylene chloride as well as in low polar polymermatrices such as methyl polymethacrylate. The small level of aggregationof the molecules of this anionic coloring material with one anotherprevents a phenomenon of widening of the optical absorption bands ofthis coloring material.

EXAMPLE 22

18.13 g (50 mmoles) of polyoxyethylene-23 lauryl ether (Brij® 30)C₁₂H₂₅(OCH₂CH₂)OH and 3.93 g (25 mmoles, commercially available fromAldrich) of 1,2,3-triazole-4,5-dicarboxylic in admixture of 30 ml of THFand 10 ml of pyridine were reacted in the presence of 1.03 g (50 mmoles)of 1,3-dicyclohexylcarbodiimide. After 48 hours, the reaction mixturewas filtered to remove the precipitate of dicyclohexylurea, and it wasstirred in the presence of 5 g of lithium carbonate Li₂CO₃. After 48hours, the reaction mixture was filtered to remove the excess of lithiumcarbonate and the solvent was evaporated. 20.5 g of the followingcompound were recovered:

This salt is an excellent surfactant. At a concentration as low as 0.1g/l in water, the surface tension was decreased to a value lower than 20mN/m.

EXAMPLE 23

2.54 g of polyaniline chloride (AC&T, St Égrève, France) were suspendedin 100 ml of water:

There is then added 9.51 g of potassiumtrifluoromethanesulfonyl(di-2-ethylhexylaminosulfonyl)imide obtained inExample 15:

After 48 hours under stirring, a polyaniline doped withdi-2-ethylhexylaminosulfonyl-4,5-dicyanoimidazole was recovered. In thisform, it is soluble in toluene and it was possible to produce a filmfrom this solution. The thus-doped polyaniline is an electronicallyconductive polymer which has a conductivity, measured by the method offour points, of 5 S/cm, which is stable in humid medium.

From this solution it was also possible to produce a film on a supportof polypropylene (PP) treated by Corona effect. After drying undervacuum at 60° C. during 48 hours, a conductive deposit was obtainedwhich adheres to polyaniline, and has a thickness lower than one micron.This type of treatment on plastic materials is particularly interestingfor producing flexible electrical contactors or systems ofelectromagnetic protections. In addition, this electronically conductivepolymer is a good corrosion inhibitor of ferrous metals and aluminum inacid or chloride medium.

EXAMPLE 24

In a three neck flask provided with a cooler, a mechanical stirrer and aneutral gas inlet (Argon), 9.5 g of a copolymer of dimethylsiloxane and(hydrogeno)(methyl)-siloxane (HMS 301 25% SiH, M_(w) 1900 Gelest Inc.,Tullytown, Pa., USA) were suspended in tetrahydrofurane. 7.04 g oflithium 2-(4-ene-1,1-difluorobutyl)-5-cyano-1,3,4-triazole, prepared asin Example 2, and 70 mg of chloroplatinic acid H₂PtCl₆ were then added.The mixture was heated to reflux during 4 hours. The polymer was thenreprecipitated in ethanol.

This polymer is soluble in most organic solvents, including inamounts >2% in oils or silicon materials, thus giving them antistaticproperties.

EXAMPLE 25

10 mmoles of potassium 2-perfluorobutanesulfonyl-4,5-dicyanoimidazole,obtained in Example 4, and 10 mmoles of di-4,4′-dodecylphenyliodonium(commercially available from General Electric) were stirred togetherduring 24 hours in water. By extraction of the aqueous phase withdichloromethane, the following compound was recovered in quantitativeyield after evaporation of dichloromethane and drying:

This salt enables to initiate under the effect of actinic radiation(light, γ rays, electron beams) the cationic cross-linking of monomersrich in electrons (vinyl ethers, alkyl vinyl ethers, . . . ). It issoluble in most of the usual organic solvents (tetrahydrofurane,acetonitrile, dimethylformamide, ethyl acetate, glymes, . . . ) and inaprotic solvating polymers such as poly(ethylene oxide). It is alsosoluble at more that 10% by weight in reactive solvents such astriethyleneglycol divinyl ether.

The photoinitiating properties of this salt were tested by irradiatingwith U.V. radiation at 254 nm, and a power of 1,900 mW/cm², atriethyleneglycol divinyl ether solution containing 1% by weight of thissalt. After a few seconds under irradiation, the reactive solventsolidified, this reaction being very exothermic.

EXAMPLE 26

4.08 (20 mmoles) of potassium 3,5-bis(trifluoromethyl)pyrazole(commercially available from Aldrich) in 50 ml of anhydrous THF werereacted with 2.17 g (20 mmoles) of 1-chloro-1-ethoxyethane (preparedaccording to the procedure described by Grummitt & al., OrganicSynthesis, Wiley, New-York, 1963, Collect. Vol. IV, p 748). After 48hours under stirring, the reaction mixture was centrifuged to remove theprecipitate of potassium chloride KCl. There were then added 8.92 g ofperfluoro(4-methyl-3,6-dioxaoct-7-ene)sulfonyl fluoride (commercializedby Apollo Scientific Limited, Stockport, England) and 4.05 g (40 mmoles)of freshly distilled triethylamine. The reaction mixture was thenbrought to 60° C. during 72 hours and the solvent was evaporated. Theresidue was recrystallized in 30 ml of water saturated with potassiumchloride. After drying, the following compound was recovered:

The corresponding acid was obtained by extracting with ether an aqueoussolution of this potassium salt acidified with hydrochloric acid.

A porous GORE-TEX® textile of a thickness of 100 μm, commerciallyavailable from Gore, was impregnated with a concentrated dichloromethanesolution of said acid containing cyanovaleric acid as polymerizationinitiator. After evaporation of the solvent, the acid washomopolymerized within the textile matrix by keeping, under argon, thetemperature of the mixture at 60° C. during 24 hours. The membrane thusobtained was used as an electrolyte in a test cell of ahydrogen/methanol polymer electrolyte combustible battery. The life ofthis membrane was longer than 1,000 hours, with a lower permeability tomethanol than the one obtained by utilizing a membrane of Nafion® 117(commercially available from Dupont de Nemours) of the same thickness.Such a membrane may also be used for the Friedel-Crafts heterogeneouscatalysis of the acylation reaction of toluene with benzoyl chloride.

EXAMPLE 27

To 10 mmoles of lithium 4-pentafluoro-ethyl-5-cyano-1,2,3-triazole,obtained in Example 12, in solution in 10 ml of water, there is added 12mmoles of 1-ethyl-3-methyl-1H-imidazolium chloride (commerciallyavailable from Aldrich).

There is obtained a liquid phase which is denser than water. This phasewas recovered by extraction with dichloromethane. After evaporation ofdichloromethane and drying under vacuum at 40° C. of the liquidobtained, the following liquid salt was recovered:

This molten salt has a conductivity of 4.3×10⁻³ S⁻¹.cm⁻¹ and a freezingpoint lower than −10° C. Its wide range of redox stability makes it anelectrolyte which is particularly interesting for electrochemicalgenerators such as lithium batteries, supercapacitances, systems ofmodulation of light, photovoltaic cells.

An electrochemical photovoltaic cell similar in principle to the onedescribed in European Patent EP 613466 was prepared. For this purpose, asystem made of two electrodes separated by a vacuum space of a thicknessof 30 μm was assembled. The first electrode was coated with ananoparticular layer of titanium dioxide TiO₂ 0.25 Jim thick on whichcis-dithiocyanato-bis-(2,2′-bipyridyl-4,4′-dicarboxylate ruthenium (II)was adsorbed as sensitizer. The space between the electrodes was filledwith an electrolyte made of the molten salt in which 10% by weight ofmethylhexyl imidazolium iodide and 10 mmoles of iodine were solubilized.With this photovoltaic cell there are obtained interesting performances,and in particular a short-circuit current of 69 μA.cm⁻² and a voltage inopen circuit of 512 mV.

This liquid salt may also be used as electrolyte in electrochemicalsupercapacitances utilizing electrodes of activated carbon or compositeelectrodes obtained from metallic fibers and carbon fibers treated inreducing atmosphere.

EXAMPLE 28

To 3.2 g (25 mmoles) of 2-(3-thienyl)ethanol in 60 ml of anhydrousdimethylformamide, there is added 7.26 g (25 mmoles) of potassium1-vinylsulfonyl-2,5-trifluoromethyl-3,4-dicyano-cyclopentadiene,obtained by a process similar to the one described in Example 19, byreplacing 4-styrenesulfonyl chloride with ethylenesulfonyl fluoride(commercially available from ACROS), 3.46 g of anhydrous potassiumcarbonate K₂CO₃ (25 mmoles) and 330 mg (1.25 mmoles) of a crown-ether,which is 18-Crown-6 (acting as complexing agent of the potassiumcation). The reaction mixture was then stirred under argon at 85° C.After 48 hours, the reaction mixture was filtered on a fritted glass ofporosity N° 3, and the solvent was evaporated under reduced pressure.After drying, the compound was recrystallized in 20 ml of watercontaining 1.86 g (25 mmoles) of anhydrous potassium chloride KCl. Afterfiltration and drying, the following compound was recovered:

10 ml of a 5×10⁻² M solution of said compound in acetonitrile wereprepared and an electropolymerization was carried out in the anodecompartment in an electrochemical cell, on the platinum electrode. Thereis obtained a flexible conductor film of:

in which doping (oxidation) is ensured by exchange of cations andelectrons with the exterior. The conductivity of this material, stableat ambient atmosphere and in humid medium, is of the order of 10 S.cm⁻¹.The electropolymerization carried out in the presence of non-substitutedpyrrol or a pyrrol having oxyethylene chains in N or 3 position givescopolymers which are equally stable in which the change of color may beused to constitute electrochrome systems.

EXAMPLE 29

Catalysis of an Aldolic Condensation

The catalytic effect of the scandium salt of3-trifluoromethyl-5-trifluoromethanesulfonyl-1,2,4-triazole, obtained inExample 3, towards an aldolic condensation was evaluated in thefollowing manner: To a solution containing 339 mg (0.4 mmoles) of thescandium salt of3-trifluoromethyl-5-trifluoromethanesulfonyl-1,2,4-triazole (10% molar)in 15 ml of dichloromethane, there is added a mixture of 1.05 mg (6mmoles) of 1-ene-2-methyl-1-silylacetal-1-methoxypropene(CH₃)₂C═C(OSiMe₃)OMe and 420 mg (4 mmoles) of benzaldehyde in 10 ml ofdichloromethane. After 16 hours under stirring at room temperature,water was added and the product was extracted with dichloromethane. Theorganic phase was washed with three fractions of 100 ml of water, anddichloromethane was evaporated. The residue was then treated with atetrahydrofurane/HCl 1 M (20:1) mixture during 0.5 hours at 0C. Afterdiluting with hexane, a saturated solution of sodium bicarbonate wasadded and the product was extracted with dichloromethane. The organicphase was washed with a saturated solution of sodium chloride, and itwas dried with sodium sulfate. After evaporation of the solvents, theraw product was chromatographed on silica gel.Methyl-3-hydroxy-2,2-dimethyl-phenylpropionate was obtained with a yieldof 90%.

EXAMPLE 30

Catalysis of a Michael Addition

The catalytic effect of the scandium salt of3-trifluoromethyl-5-trifluoromethanesulfonyl-1,2,4-triazole, obtained inExample 3, with respect to a Michael addition was evaluated in thefollowing manner. To a solution of 339 mg (0.4 mmoles) of scandium3-trifluoromethyl-5-trifluoromethanesulfonyl-1,2,4-triazole (10% molar)in 15 ml of dichloromethane, there is added a mixture of 1.05 g (6mmoles) of 1-ene-2-methyl-1 -silylacetal-1-methoxypropene(CH₃)₂C═C(OSiMe3)OMe and 840 mg (4 mmoles) of chalcone in 10 ml ofdichloromethane. After 12 hours under stirring at room temperature,water is added and the product was extracted with dichloromethane. Theorganic phase was washed with three fractions of 100 ml of water, anddichloromethane was evaporated. The residue was then treated with atetrahydrofurane/HCl 1 M (20:1) mixture during 0.5 hours at 0° C. Afterdiluting with hexane, a saturated solution of sodium bicarbonate wasadded, and the product was extracted with dichloromethane. The organicphase was washed with a saturated solution of sodium chloride, and driedwith sodium sulfate. After evaporation of these solvents, the rawproduct was chromatographed on silica gel. There is obtained a1,5-dicarbonylated compound with a yield of 89%.

EXAMPLE 31

Catalysis of a Friedel-Crafts Reaction of Acylation

The catalytic effect of the scandium salt of3-trifluoromethyl-5-trifluoromethanesulfonyl-1,2,4-triazole, obtained inExample 3, relative to a reaction was evaluated in the following manner.In 40 ml of anhydrous nitromethane, there is added 592 mg (700 μmoles)of the scandium salt of3-trifluoromethyl-5-trifluoromethanesulfonyl-1,2,4-triazole, and 1.08 g(10 mmoles) of anisol and 2.04 g of acetic anhydride. After stirringduring 10 min at 21° C., the reaction mixture was diluted with 50 ml ofether and the reaction was inhibited by 100 ml of a saturated solutionof sodium bicarbonate NaHCO₃. After filtration on Celite, the solutionwas extracted with three fractions of 50 ml ether, and the collectedether phase was washed with a saturated solution of potassium chloride.After drying the ether phase with magnesium sulfate and evaporation,1.46 g of p-methoxyacetophenone (97% yield) was collected, with a puritycharacterized by a proton RMN higher than 99%.

EXAMPLE 32

According to a process similar to the one described in Example 4, thepotassium salt of 2-(1R)-(−)-10-camphorsulfonyl-4,5-dicyanoimidazole wasobtained by substituting perfluorobutanesulfonyl fluoride with(1R)-(−)-10-camphorsulfonyl (commercially available from Aldrich).

The corresponding lithium salt was obtained by ionic exchange(metathesis) in tetrahydrofurane with lithium chloride.

The scandium salt was obtained by treating the potassium salt with astoichiometric quantity of scandium tetrafluoroborate Sc(BF₄)₃ inacetonitrile. After filtration to remove the precipitate of potassiumtetrafluoroborate KBF₄ and evaporation of the solvent, the followingcompound was recovered in quantitative yield;

This salt was used as catalyst in a Diels-Alder reaction, namely areaction of methylvinylketone with cyclopentadiene.

To a solution of 651 mg (10 mmoles) of freshly distilled cyclopentadieneand 701 mg (10 mmoles) of methylvinylketone in 10 ml of dichloromethanethere is added 200 μmoles of the chiral scandium salt. After 24 hours atroom temperature, the reaction mixture was filtered to remove thecatalyst in suspension. The yield of the reaction, determined bychromatography in gaseous phase, is higher than 85%. After separatingthe various products of the reaction on a chiral column, theenantiomeric excesses were determined by RMN, which has revealed anenantiomeric excess of 73%.

EXAMPLE 33

The lithium salt of 4,5-trifluoromethyl-1,2,3-triazole, obtained inExample 12, was tested in electrochemical generators of lithium-polymertechnology.

A battery was produced by superposing the following layers:

a current collector of stainless steel having a thickness of 2 mm;

a cathode consisting of a pastil of a film of composite material havinga thickness of 72 μm and comprising vanadium dioxide (45% by volume),Shawinigan black (5% by volume) and polyethylene oxide of molecularweight M_(w)=3×10⁵ (50% by volume);

an electrolyte consisting of a pastil of a poly(ethylene oxide) film ofmolecular weight M_(w)=5×10⁶ containing said lithium salt at aconcentration O/Li=15/1:

an anode made of a sheet of metallic lithium having a thickness of 50μm;

a current collector analogous to the above collector.

The pastils constituting the electrode and electrolyte were cut out in aglove box and piled in the order indicated above. The collectors werethen placed on either side of the pile obtained. The assembly was sealedin a housing for a button-shaped battery which simultaneously enables toprotect the generator from the atmosphere and to exercise a mechanicalstress on the films. The battery was then placed in an enclosure underargon mounted in a drying oven at a temperature of 60° C. It wasthereafter cycled between 1.8 and 3.3 V at a rate of charge/discharge ofC/10 (nominal capacity charged or discharged in 10 hours). The cyclingcurve obtained is given in FIG. 1, on which the utilization u, expressedin %, is given in ordinate, and the number of cycles, C, is given inabscissae.

Similar performances were obtained by utilizing:

the lithium salt of 4-trifluoromethyl-5-cyano-1H-1,2,3-triazole obtainedin Example 12;

the lithium salt of 2-cyano-5-trifluoromethyl-1,3,4-triazole obtained inExample 1;

the lithium salt of2-trifluoromethanesulfonyl-5-trifluoromethyl-1,3,4-triazole obtained inExample 3;

the lithium salt of 2-dimethylaminosulfonyl-4,5-dicyanoimidazoleobtained in Example 14;

the lithium salt of1-fluoro-2,5-trifluoromethyl-3,4-dicyanocyclopentadiene obtained inExample 17;

the polysalt of lithium ofpoly(2-(3,4-epoxy-1,1-difluorobutane)-5-cyano-1,3,4-triazole) obtainedin Example 6. In the latter case, the polysalt is introduced at aconcentration O/Li=25/1 in the electrolyte and in the cathode. It waspossible to note better performances during calls for power due to thefact of the utilization of fixed anions. The utilization of fixed anionsalso enabled to improve the evolution of the interface resistance.

What is claimed is:
 1. An ionically conductive material comprising anionic compound in a solvent, the said compound comprising at least oneanionic part associated to at least one cationic part M in sufficientnumber to ensure the electronic neutrality of the whole, wherein M is ahydroxonium, a nitrosonium NO⁺, an ammonium —NH₄ ⁺, a metallic cationhaving a valency m, an organic cation having a valency m, or anorganometallic cation having a valency m and in that the anionic part ispentacyclic or derived from tetrazapentalene and corresponds to thefollowing formula:

in which the groups X₁ is —N═, X₂ is —N═, X₃ is —C(Y_(c))— with Y_(c)being C_(n)F_(2n+1), X₄ is —N—, and X₅ is —C(Y_(c))— with Y_(c) beingSO₂Q—, and: Q is a radical selected from: alkyl or alkenyl radicals,aryl, arylalkyl, alkylaryl or alkenylaryl radicals, alicyclic orheterocyclic radicals, including polycyclic radicals, said radicalsbeing optionally halogenated or perhalogenated and/or optionallycarrying at least one other, thioether, amine, imine, amide, carboxyl,carbonyl, isocyanate, isothiocyanate, hydroxy functional group.
 2. Amaterial according to claim 1, characterized in that the organic cationis selected from a group consisting of cations R₃O⁺, NR₄ ⁺, RC(NHR₂)₂ ⁺,C(NHR₂)₃ ⁺, C₅R₆N⁺, C₃R₅N₂ ⁺, C₃R₇N₂ ⁺, C₂R₄N₃ ⁺, SR₃ ⁺, PR₄ ⁺, IR₂ ⁺,(C₆R₅)₃C⁺, the radicals R independently representing an H or a radicalselected from the group consisting of: alkyl, alkenyl, oxa-alkyl,oxa-alkenyl, aza-alkyl, aza-alkenyl, thiaalkyl, thia-alkenyl,sila-alkyl, sila-alkenyl, aryl, arylalkyl, alkylaryl, alkenylaryl,dialkylamino and dialkylazo radicals; cyclic or heterocyclic radicalsoptionally comprising at least one lateral chain comprising heteroatomssuch as nitrogen, oxygen, sulfur; cyclic or heterocyclic radicalsoptionally comprising heteroatoms in the aromatic nucleus; groupscomprising a plurality of aromatic or heterocyclic nuclei, condensed ornon-condensed, optionally containing at least one nitrogen, oxygen,sulfur or phosphorus atom; with the proviso that a plurality of radicalsR may together form aliphatic or aromatic cycles optionally enclosingthe center carrying the cationic charge.
 3. A material according toclaim 2, characterized in that the onium cation is part of the Y_(c) orthe substituent Q.
 4. A material according to claim 2, characterized inthat the onium cation is part of a recurring unit of a polymer.
 5. Amaterial according to claim 2, characterized in that the cation M is acationic heterocycle with aromatic character, including at least onealkylated nitrogen atom in the cycle.
 6. A material according to claim5, characterized in that the cation is an imidazolium, an imidazolinium,a triazolium, a pyridinium, a 4-dimethylaminopyridinium, said cationsoptionally carrying a substituent on the carbon atoms of the cycle.
 7. Amaterial according to claim 2, characterized in that the cation M is agroup having a bond —N═N—, —N═N⁺, a sulfonium group, an iodonium group,or a substituted or non-substituted arene-ferrocenium cation, optionallyincorporated in a polymeric network.
 8. A material according to claim 2,characterized in that the cation is a diaryliodonium cation, adialkylaryliodonium cation, a triarylsulfonium cation, a trialkylarylsulfonium cation, or a substituted or non-substituted phenacyl-dialkylsulfonium cation.
 9. A material according to claim 8, characterized inthat the cation is part of a polymer chain.
 10. A material according toclaim 2, characterized in that M is an organic cation including a group2,2′-[azobis(2-2′-imidazolinio-2-yl)propane]²⁺ or2,2′-azobis(2-amidiniopropane)²⁺.
 11. A material according to claim 1characterized in that the cation M is a metallic cation selected fromthe group consisting of cations of alkali metals, cations of alkaliearth metals, cations of transition metals, cations of trivalent metals,cations of rare earths and organometallic cations.
 12. A materialaccording to claim 1, characterized in that the cation is ametallocenium, selected from the group consisting of cations derivedfrom ferrocene, titanocene, zirconocene, indenocenium cations, arenemetallocenium cations, cations of transition metals complexed withphosphine ligands optionally having a chirality and organometalliccations having one or more alkyl or aryl groups covalently fixed to anatom or a group of atoms, said cations optionally being part of apolymeric chain.
 13. A material according to claim 1, characterized inthat the substituent Q is selected from alkyl, alkenyl, oxa-alkyl,oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl or thia-alkenyl having 1to 24 carbon atoms, or from aryl, arylalkyl, alkylaryl or alkenylarylhaving 5 to 24 carbon atoms, or from alkyl or alkenyl radicals having 1to 12 carbon atoms and optionally comprising at least one heteroatom O,N or S in the main chain or in a lateral chain, and/or optionallycarrying a hydroxy group, a carbonyl group, an amine group, a carboxylgroup.
 14. Ionically conductive material according to claim 1,characterized in that at least one of the substituents Y_(c) is arecurring unit of a polymer.
 15. Ionically conductive material accordingto claim 1, characterized in that the solvent is either an aproticliquid solvent, selected from linear ethers and cyclic ethers, esters,nitriles, nitro derivatives, amides, sulfones, sulfolanes, sulfamidesand partially halogenated hydrocarbons, or a polar polymer, or a mixturethereof.
 16. Ionically conductive material according to claim 15,characterized in that the solvent is a solvating polymer, cross-linkedor non-cross-linked, which may carry grafted ionic groups.
 17. Ionicallyconductive material according to claim 16, characterized in that thesolvating polymer is selected from polyethers of linear structure, combor blocks, which may form a network based on poly(ethylene oxide),copolymers containing the ethylene oxide or propylene oxide orallylglycidylether units, polyphosphazenes, cross-linked networks basedon polyethylene glycol cross-linked with isocyanates, networks obtainedby polycondensation and carrying groups which enable the incorporationof cross-linkable groups and block copolymers in which certain blockscarry functions with redox properties.
 18. Ionically conductive materialaccording to claim 1, characterized in that the solvent essentiallyconsists of an aprotic liquid solvent and a polar polymer solventcomprising units containing at least one heteroatom selected fromsulfur, oxygen, nitrogen and fluorine.
 19. Ionically conductive materialaccording to claim 18, characterized in that the polar polymer mainlycontains units derived from acrylonitrile, vinylidene fluoride,N-vinylpyrrolidone or methyl methacrylate.
 20. Ionically conductivematerial according to claim 1, characterized in that it additionallycontains at least one second salt.
 21. Ionically conductive materialaccording to claim 1, characterized in that it additionally contains amineral or organic filler in the form of powder or fibers. 22.Electrochemical generator comprising a negative electrode and a positiveelectrode both separated by an electrolyte, characterized in that theelectrolyte is a material according to claim
 1. 23. Generator accordingto claim 22, characterized in that the negative electrode consists ofmetallic lithium, or an alloy thereof, optionally in the form ofnanometric dispersion in lithium oxide, or a double nitride of lithiumand a transition metal, or an oxide with low potential having thegeneral formula Li_(1+y+x/3)Ti_(2−x/3)O₄ (0≦x≦1, 0≦y≦1), or carbon andcarbonated products produced by pyrolysis of organic material. 24.Generator according to claim 22, characterized in that the positiveelectrode is selected from vanadium oxides VO_(x) (2≦x≦2.5), LiV₃O₈,Li_(y)Ni_(1−x)Co_(x)O₂, (0≦x≦1; 0≦y≦1), spinels of manganeseLi_(y)Mn_(1−x)M_(x)O₂ (M=Cr, Al, V, Ni, 0≦x≦0.5; 0≦y≦2), organicpolydisulfides, FeS, FeS₂, iron sulfate Fe₂(SO₄)₃, phosphates andphosphosilicates of iron and lithium of olivine structure, orsubstituted products wherein iron is replaced by manganese, used aloneor in mixtures.
 25. Generator according to claim 22, characterized inthat the cathode collector is made of aluminum.
 26. Supercapacitorutilizing at least one carbon electrode with high specific surface, oran electrode containing a redox polymer, in which the electrolyte is amaterial according to claim
 1. 27. A process for doping, p or n, apolymer with electronic conduction, said process comprising utilizing amaterial according to claim
 1. 28. Electronically conductive materialcharacterized in that it comprises a material according to claim
 1. 29.Process of polymerization or cross-linking of monomers or prepolymerscapable of cationic reaction, characterized in that there is used amaterial according to claim 1 as photoinitiator constituting a source ofacid catalyzing the reaction.
 30. Process according to claim 29,characterized in that the monomers are selected from the groupconsisting of compounds which include a cyclic ether function, a cyclicthioether function or a cyclic amino function, vinyl compounds, vinylethers, oxazolines, lactones and lactames.
 31. Process according toclaim 29, characterized in that the prepolymer is selected from thegroup consisting of compounds in which epoxy groups are carried by analiphatic chain, an aromatic chain, or a heterocyclic chain.
 32. Processaccording to claim 29, characterized in that it consists in mixing thephotoinitiator with at least one monomer or prepolymer capable ofcationic polymerization and subjecting the mixture obtained to actinicradiation.
 33. Process according to claim 32, characterized in that thereaction mixture is subject to radiation after having been formed into athin layer.
 34. Process according to claim 29, characterized in that thephotoinitiator is used in the form of a solution in a solvent which isinert towards the polymerization reaction.
 35. Process according toclaim 34, characterized in that the inert solvent is selected from thegroup consisting of acetone, methylethyl ketone, acetonitrile, propylenecarbonate, γ-butyrolactone, ether-esters of mono-, di-, tri-ethylene orpropylene glycols, ether-alcohols of mono-, di-, tri-ethylene orpropylene glycols, esters of phthalic acid or of citric acid. 36.Process according to claim 29, characterized in that the reaction iscarried out in the presence of a solvent or a diluent consisting of acompound which is reactive towards polymerization.
 37. Process accordingto claim 36, characterized in that the reactive compound is selectedfrom the group consisting of vinyl mono- and di- ethers of mono-, di-,tri-, tetra-ethylene or propylene glycols, trivinyl ethertrimethylolpropane and divinyl ether of dimethanolcyclohexane,N-vinylpyrolidone, 2-propenylether of propylene carbonate.
 38. Processaccording to claim 29, characterized in that a photosensitizer is addedto the reaction mixture.
 39. Process according to claim 38,characterized in that the photosensitizer is selected from the groupconsisting of anthracene, diphenyl-9,10-anthracene, perylene,phenothiazine, tetracene, xanthone, thioxanthone, isopropylthioxanthone,acetophenone, benzophenone, 1,3,5-triaryl-2-pyrazolines and derivativesthereof.
 40. Process according to claim 29, characterized in that thereaction mixture additionally contains at least one monomer orprepolymer capable of free radical polymerization and a compound capableof releasing a free radical polymerization initiator under the effect ofactinic radiation or β radiation or under the action of heat. 41.Process of modifying properties of solubility of a polymer having groupssensitive towards acids, characterized in that it consists in subjectingsaid polymer to actinic radiation or β radiation, in the presence of anionically conductive material comprising an ionic compound in a solvent,the said compound comprising at least one anionic part associated to atleast one cationic part M in sufficient number to ensure the electronicneutrality of the whole, wherein M is a hydroxonium, a nitosonium NO⁺,an ammonium —NH₄ ⁺, a metallic cation having a valency m, an organiccation having a valency m, or an organometallic cation having a valencym and in that the anionic part is pentacyclic or derived fromtetrazapentalene and corresponds to one of the following formulae:

in which the groups —X_(i)— represent independently from one another agroup selected from —N═, —N—, —C(Y_(c))═, —C(Y_(c))—, —S(═O)(Qs)═,—S(Qs)═ or —P(Q′)(Q″)═, wherein among the five groups —X_(i)— formingthe ring, no —X_(i)— represents —N═or —N⁻,or at least two —X_(i)—represent independently —N═or —N⁺—, at most four groups —X_(i)— comprisean hydrogen atom, at most two groups —X_(i)— comprise a sulfur atomprovided they are not adjacent on the ring, at most one group —X_(i)—comprise a phosphorus atom, and: Q′ and Q″ represent independently fromone another a C₁-C₈ perhaloalkyl or perhaloalkenyl radical a C₆-C₁₂ arylor alkylaryl radical, optionally halogenated, each may contain oxa,thia, aza substituents; Qs is a radical selected from: a) alkyl oralkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals,alicyclic or heterocyclic radicals, including polycyclic radicals, saidradicals being optionally halogenated or perhalogenated and/oroptionally carrying at least one ether, thioether, amine, imine, amide,carboxyl, carbonyl, isocyanate, isothiocyanate, hydroxy functionalgroup; b) monocyclic, polycyclic or condensed aromatic radicals in whichthe aromatic nuclei and/or at least one substituent of a nucleuscomprise heteroatoms; c) polymer radicals; d) radicals having one ormore cationic ionophoric groups and/or one or more anionic ionophoricgroups; Y_(c) or Y represent II, or a group attracting electronsselected from the group consisting of: F, Cl, Br, —C≡N, —S—C≡N, —N═C═S,—N═C═O, —NO₂, C_(n)F_(2n+1)—C_(n)F_(2n+1)—O—, C_(n)F_(2n+1)—CH₂—,—OC₂F₄H, —SCF₃, —SC_(n)F_(2n+1), —SC₂F₄H, —O—CF═CF₂, —SCF═CF₂, FSO₂;radicals QSO₂—, —CO₂Q, Q—N—SO₂—, QCO—, in which Q is selected from thesubstituents defined above for Q_(s); radicals comprising one or morearomatic nuclei optionally containing at least one nitrogen, oxygen,sulfur or phosphorus atoms, said nuclei may optionally be condensednuclei and/or the nuclei may optionally carry at least one substituentselected from halogens, —CN, —NO₂, —SCN, —N₃, CF₂═CF—O—, radicals R_(F)—and R_(F)CH₂— in which R_(F) is a perfluoroalkyl radical having 1 to 12carbon atoms, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl,alkenyl, oxa-alkyl, oxaalkenyl, aza-alkyl, aza-alkenyl, thia-alkyl,thia-alkenyl radicals, polymer radicals, radicals having at least onecationic ionophoric group and/or at least one anionic ionophoric group;or two substituents selected from Y_(c), Q_(s), Q′ and Q″ of apentacyclic anionic group on the one hand, or two substituents Y of ananionic group derived from tetrazapentalene on the other hand, togetherform a ring having 4 to 8 chains, said ring optionally being of aromaticconjugated nature; or one of the substituents Y, Y_(c) or Q_(s) is amultivalent radical (including a dendrimer) connected to at leastanother pentacyclic anionic group or to at least another anionic groupderived from tetrazapentalene; or one of the substituents Y, Y_(c) orQ_(s) represent a recurring unit of a polymer.
 42. Process according toclaim 41, characterized in that the polymer contains ester units orarylether units derived from a tertiary alcohol.
 43. Process accordingto claim 42, characterized in that the polymer is selected from thegroup consisting of homopolymers and copolymers of tert-butyl ortert-amyl, (tert-butoxycarbonyloxystyrene) or(tert-amyloxystyrene)itaconate.
 44. Process according to claim 41,characterized in that it is used for the chemical amplification ofphotoresists.
 45. A laser or optical disk containing a composition orphotographic film having a sensitizer containing a composition in whichthe composition contains cationic coloring material, characterized inthat it contains an ionically conductive material comprising an ioniccompound, the said compound comprising at least one anionic partassociated to at least one cationic part M in sufficient number toensure the electronic neutrality of the whole, wherein M is ahydroxonium, a nitrosonium NO⁺, an ammonium —NH₄ ⁺, a metallic cationhaving a valency m, an organic cation having a valency m, or anorganometallic cation having a valency m and in that the anionic part ispentacyclic or derived from tetrazapentalene and corresponds to one ofthe following formulae:

in which the groups —X_(i)— represent independently from one another agroup selected from —N═, —N—, —C(Y_(c) )═, —C(Y_(c))—, —S(═O)(Qs)═,—S(Qs)═ or —P(Q′)(Q″)═, wherein among the five groups —X_(i)— formingthe no —X_(i)— represents —N═or —N⁻,or at least two —X_(i)— representindependently —N═or —N⁺—, ring at most four groups —X_(i)— comprise anhydrogen atom, at most two groups —X_(i)— comprise a sulfur atomprovided they are not adjacent on the ring, at most one group —X_(i)—comprise a phosphorus atom, and: Q′ and Q″ represent independently fromone another a C₁-C₈ perhaloalkyl or perhaloalkenyl radical, a C₆-C₁₂aryl or alkylaryl radical, optionally halogenated, each may contain oxa,thia, aza substituents; Qs is a radical selected from: a) alkyl oralkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals,alicyclic or heterocyclic radicals, including polycyclic radicals, saidradicals being optionally halogenated or perhalogenated and/oroptionally carrying at least one ether, thioether, amine, imine, amide,carboxyl, carbonyl, isocyanate, isothiocyanate, hydroxy functionalgroup; b) monocyclic, polycyclic or condensed aromatic radicals in whichthe aromatic nuclei and/or at least one substituent of a nucleuscomprise heteroatoms; c) polymer radicals; d) radicals having one ormore cationic ionophoric groups and/or one or more anionic ionophoricgroups; Y_(c) or Y represent H, or a group attracting electrons selectedfrom the group consisting of: F, Cl, Br, —C≡N, —S—C≡N, —N═C═S, —N═C═O,—NO₂, C_(n)F_(2n+1)—C_(n)F_(2n+1)—O—, C_(n)F_(2n+1)—CH₂—, —OC₂F₄H,—SCF₃, —SC_(n)F_(2n+1), —SC₂F₄H, —O—CF═CF₂, —SCF═CF₂, FSO₂; radicalsQSO₂—, —CO₂Q, Q—N—SO₂—, QCO—, in which Q is selected from thesubstituents defined above for Q_(s); radicals comprising one or morearomatic nuclei optionally containing at least one nitrogen, oxygen,sulfur or phosphorus atoms, said nuclei may optionally be condensednuclei and/or the nuclei may optionally carry at least one substituentselected from halogens, —CN, —NO₂, —SCN, —N₃, CF₂═CF—O—, radicals R_(F)—and R_(F)CH₂— in which R_(F) is a perfluoroalkyl radical having 1 to 12carbon atoms, fluoroalkyloxy groups, fluoroalkylthioxy groups, alkyl,alkenyl, oxa-alkyl, oxaalkenyl, aza-alkyl, aza-alkenyl, thia-alkyl,thia-alkenyl radicals, polymer radicals, radicals having at least onecationic ionophoric group and/or at least one anionic ionophoric group;or two substituents selected from Y_(c), Q_(s), Q′ and Q″ of apentacyclic anionic group on the one hand, or two substituents Y of ananionic group derived from tetrazapentalene on the other hand, togetherform a ring having 4 to 8 chains, said ring optionally being of aromaticconjugated nature; or one of the substituents Y, Y_(c) or Q_(s) is amultivalent radical (including a dendrimer) connected to at leastanother pentacyclic anionic group or to at least another anionic groupderived from tetrazapentalene; or one of the substituents Y, Y_(c) orQ_(s) represent a recurring unit of a polymer.
 46. A laser or opticaldisk or photographic film of cationic coloring material according toclaim 45, characterized in that the negative charge(s) of thepentacyclic anionic group or derived from tetrazapentalene are eitherfixed to the molecule of coloring material, or they constitute thecounter-ion of positive charge of the coloring material.
 47. A processof using an ionic compound in a catalytic reaction, said reactionselected from the group consisting of Friedel-Craft reactions, reactionsof Diels and Alder, Michael additions, reactions of allylation,reactions of pinacolic coupling, reactions of glycosilation, reactionsof openings of cycles of oxetanes, reactions of aldolization, reactionsof metathesis of alkenes, Ziegler-Natta polymerizations, ring openingmetathesis polymerizations and metathesis polymerizations of acyclicdienes, said process comprising adding a material of claim 1 to areaction mixture.
 48. A process according to claim 47, characterized inthat the compound in the material is a compound according to claim 1 inwhich the cation is selected from lithium, magnesium, copper, zinc, tin,trivalent metals, including rare earths, platinoids, and organometalliccations.
 49. Electrochrome device in which the electrolyte is anionically conductive material comprising an ionic compound in a solvent,the said compound comprising at least one anionic part associated to atleast one cationic part M in sufficient number to ensure the electronicneutrality of the whole, wherein M is a hydroxonium, a nitrosonium NO⁺,an ammonium —NH₄ ⁺, a metallic cation having a valency m, an organiccation having a valency m, or an organometallic cation having a valencym and in that the anionic part is pentacyclic or derived fromtetrazapentalene and corresponds to one of the following formulae:

in which the groups —X_(i)— represent independently from one another agroup selected from —N═, —N—, C(Y_(c))═, —C(Y_(c))—, —S(═O)(Qs)═,—S(Qs)═ or —P(Q′)(Q″)═, wherein among the five groups —X_(i) — formingthe ring, no —X_(i)— represents —N═ or —N⁻, or at least two —X_(i)—represent independently —N═ or —N⁺, at most four groups —X_(i) —comprise an hydrogen atom, at most two groups —X_(i)— comprise a sulfuratom provided they are not adjacent on the ring, at most one group—X_(i)— comprise a phosphorus atom, and: Q′ and Q″ representindependently from one another a C₁-C₈ perhaloalkyl or perhaloalkenylradical, a C₆-C₁₂ aryl or alkylaryl radical, optionally halogenated,each may contain oxa, thia, aza substituents; Qs is a radical selectedfrom: a) alkyl or alkenyl radicals, aryl, arylalkyl, alkylaryl oralkenylaryl radicals, alicyclic or heterocyclic radicals, includingpolycyclic radicals, said radicals being optionally halogenated orperhalogenated and/or optionally carrying at least one ether, thioether,amine, imine, amide, carboxyl, carbonyl, isocyanate, isothiocyanate,hydroxy functional group; b) monocyclic, polycyclic or condensedaromatic radicals in which the aromatic nuclei and/or at least onesubstituent of a nucleus comprise heteroatoms; c) polymer radicals; d)radicals having one or more cationic ionophoric groups and/or one ormore anionic ionophoric groups: Y_(c) or Y represent H, or a groupattracting electrons selected from the group consisting of: F, Cl, Br,—C≡N, —S—C≡N, —N═C═S, —N═C═O, —NO₂, C_(n)F_(2n+1)—C_(n)F_(2n+1)—O—,C_(n)F_(2n+1)—CH₂—, —OC₂F₄H, —SCF₃, —SC_(n)F_(2n+1), —SC₂F₄H, —O—CF═CF₂,—SCF═CF₂, FSO₂; radicals QSO₂—, —CO₂Q, Q—N—SO₂—, QCO—, in which Q isselected from the substituents defined above for Q_(s); radicalscomprising one or more aromatic nuclei optionally containing at leastone nitrogen, oxygen, sulfur or phosphorus atoms, said nuclei mayoptionally be condensed nuclei and/or the nuclei may optionally carry atleast one substituent selected from halogens, —CN, —NO₂, —SCN, —N₃,CF₂═CF—O—, radicals R_(F)— and R_(F) CH₂— in which R_(F) is aperfluoroalkyl radical having 1 to 12 carbon atoms, fluoroalkyloxygroups, fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl, oxaalkenyl,aza-alkyl, aza-alkenyl thia-alkyl, thia-alkenyl radicals, polymerradicals, radicals having at least one cationic ionophoric group and/orat least one anionic ionophoric group; or two substituents selected fromY_(c) Q_(s), Q′ and Q″ of a pentacyclic anionic group on the one hand,or two substituents Y of an anionic group derived from tetrazapentaleneon the other hand, together form a ring having 4 to 8 chains, said ringoptionally being of aromatic conjugated nature; or one of thesubstituents Y, Y_(c) or Q_(s) is a multivalent radical (including adendrimer) connected to at least another pentacyclic anionic group or toat least another anionic group derived from tetrazapentalene; or one ofthe substituents Y, Y_(c) or Q_(s) represent a recurring unit of apolymer.